Specific embodiment
[inorganic matter laminate film]
The present invention inorganic matter laminate film sheet material (surface of its at least one party have structural cycle for 0.001 μm~100 μm of dispersed structure) the laminated organic/inorganic substance layer in the face with dispersed structure.
Fig. 1 and Fig. 2 is the ideograph in the section for an example for representing the inorganic matter laminate film of the present invention.Fig. 1 shows in pieceThe scheme of the 1 laminated organic/inorganic substance layer of face with dispersed structure of material 4 (for single layer structure), Fig. 2 are represented in sheet material 5 (for by baseThe laminate structures that material 3b and substrate layer 3a are formed) the 1 laminated organic/inorganic substance layer of face with dispersed structure scheme.Sheet material 4,5And the details of inorganic layer 2 is as described below.It it is 0.001 μm~100 μm in the structural cycle that has of at least one party of sheet materialDispersed structure face 1 on be formed with inorganic layer 2, by forming the inorganic matter laminate film of above structure, nothing can be controlledThe structure of machine nitride layer.Thus, it is possible to obtain the inorganic matter laminate film with excellent barrier properties for gases, above-mentioned inorganic matter is laminatedSheet material can use in multiple use.
It should be noted that the form as inorganic layer, however it is not limited in the whole face of sheet surface shown in Fig. 1 and 2The form of inorganic layer is set, and can also use (such as is needing barrier properties for gases in the face of sheet surface as illustrated in fig. 3Region) partly set inorganic layer form.
[sheet material]
The sheet material of the present invention is the dispersed structure that there is structural cycle to be 0.001 μm~100 μm on the surface of at least one partySheet material.
In the present invention, so-called dispersion refers to following configuration states：Ingredient different from each other of more than two kinds, which is separated into, compares moleculeThe big structure of the radius of inertia, be separated into the structure for failing to be mixed with molecular level, thus so-called dispersed structure refers toThe structure of formation.
In the present invention, as long as the structural cycle of the dispersed structure in surface is the scope of the present invention, then dispersed structure is formedConstituent, mode, realization rate can be optional, for example, both can by the organic principle comprising two or more non-compatibility orInorganic constituents, monomer or compound formed, formed alternatively, it is also possible to only be formed by organic principle, only by inorganic constituents orIt is formed by the blending constituent of organic principle and inorganic constituents.And then the ingredient of form dispersed structure a kind or more can be particleSuch ingredient with spherical shape, non-spherical, the specific shape of indefinite shape.That is, in the present invention, dispersed structure is phase separationThe upperseat concept of structure as the form other than phase separation structure, such as has resin for being dispersed with particle etc. etc. (to need what is illustratedIt is that, although having used " dispersed structure " is such to state in patent document 3, " dispersed structure " in the document is phase separation knotThe subordinate concept of structure is statement corresponding with " island structure " in the present invention).
It is so-called that there is dispersed structure on the surface of at least one party in the present invention, refer to from sheet material or substrate layer and skyThere are dispersed structures in the interface of gas or inorganic layer to the region between depth 10nm.As above-mentioned on the surface of at least one partyThe concrete mode of sheet material with dispersed structure can be enumerated：Sheet material (i) is the sheet material of the single layer structure with dispersed structure,And there is dispersed structure (for example, as shown in symbol 4 of Fig. 1) on the surface of at least one party；Sheet material (ii), be in base material at leastThe face of one side is laminated have substrate layer (its surface has dispersed structure) laminate structures sheet material (for example, 5 institute of symbol such as Fig. 2Show).Hereinafter, when the sheet material by the sheet material of single layer structure and laminate structures is needed to be inquired into distinguishing, sometimes by the formerIt is denoted as sheet material (i), the latter is denoted as to sheet material (ii).It is sheet material (i) and sheet material (ii) in addition, when being simply denoted as " sheet material "General name is the surface of sheet material (i) and the substrate layer of sheet material (ii) when similarly being recorded in a manner of as " surface of sheet material "The general name on surface.
In the present invention, the structural cycle of the dispersed structure of sheet surface is 0.001 μm~100 μm.Herein, so-called structure weekPhase is the repetitive unit that structure repeatedly is carried out with certain certain period, can pass through Flied emission scanning electron microscope(field emission type scanning electron microscopy) is evaluated.It specifically can be underThe method described in embodiment is stated to calculate.
The structural cycle of dispersed structure is 0.001 μm~100 μm, preferably 0.005 μm~50 μm, more preferably 0.01 μm~1 μm, further preferably 0.01~0.1 μm, most preferably 0.01 μm~0.03 μm.By using the above structure period, becomeThe structure of easily controllable inorganic layer is obtained, so it is preferred that.
The presence or absence of dispersed structure can be confirmed by micro- sem observation.When confirming dispersed structure, its knot can be based onThe structure period selects light microscope, scanning electron microscope (also including field emission scanning electron microscope), transmission electronMicroscope, atomic force microscope.
Then, the structural cycle of dispersed structure can be as follows obtained by electron microscope observation.AsThe phase separation structure of dispersed structure, the phase separation structure of for example, following island structures and co-continuous structure, using Fig. 4 and figure5 pairs its define and illustrate.
As an example of dispersed structure, Fig. 4 be represent dispersed structure be co-continuous structure phase separation structure when patternFigure, even if not being phase separation structure, the method that this example can be also applicable in when with such form.Specifically, in electronics10 straight lines are randomly marked in the region of square arbitrarily taken on microscopical image, obtain the straight line and phase boundaryThe intersection point in face for 10 straight lines, measures the distance between each straight line adjoining nodes, using their number average value as structurePeriod.At this point, 20 are made to report to the leadship after accomplishing a task less than the A phases of 200 and the boundary of B phases with straight line in all straight lines.
It should be noted that so-called distance is practical distance herein, the engineer's scale in the image based on electron microscopePractical distance (also identical in the following) is obtained.
As an example of dispersed structure, Fig. 5 be represent dispersed structure be island structure phase separation structure when ideograph,But even if not being phase separation structure, discontinuously disperse also be applicable in this method under such circumstances in particle etc..AsThe assay method of the above situation, can enumerate A methods as shown below and B methods, in the present invention, as long as using in A methods and B methods extremelyThe structural cycle of any one few measure decides that structural cycle is included in above range in 0.001 μm~100 μm of rangeIt is interior.
(A methods)
Carry out electron microscope observation, select in the phase separation structure of the island structure shown in symbol 9 island phase B (hereinafter,Sometimes be also referred to as island phase B) there are 10 less than the arbitrary region of 100, mark 10 straight lines in this region, obtainTo the straight line and the intersection point of boundary, for 10 straight lines, the distance between intersection point adjacent in each straight line is measured, by themNumber average value as structural cycle.At this point, make 20 boundaries less than the A phases and B phases of 200 in all straight linesIt reports to the leadship after accomplishing a task with straight line.
(B methods)
Carry out electron microscope observation, select in the phase separation structure of the island structure shown in symbol 9 island phase B (hereinafter,Sometimes it is also referred to as island phase B) there are 10 less than the predetermined region of 100, at totally 3, by the island phase B's in the regionThe number average value of size is as structural cycle.Herein, the size of so-called island phase B refers to through each island phase center of gravity from a sidePhase boundary towards the opposing party the straight line that marks of boundary in shortest straight line length.
The present invention sheet material thickness be preferably more than 50nm, less than 1,000 μm.If thinner than 50nm, nothing is being formedSometimes the structure of uncontrollable inorganic layer is influenced during machine nitride layer by the concave-convex surface of sheet material.On the other hand, if becomeThan 1,000 μ m-thick, then there are following situations：Productivity reduces；Cause sheet material warpage since stress becomes larger, be easy in inorganic matterThe defects of layer cracks.It should be noted that the thickness of sheet material can be by by transmission electron microscope (TEM), scanningThe cross-section image that type electron microscope (SEM) obtains is measured.
Particularly, preferred dispersed structure is phase separation structure in sheet material of the invention.If phase separation structure, then it is easy to shapeInto the dispersed structure of desired structural cycle, and then the structure of inorganic layer can be controlled when forming inorganic layer, easilyImprove barrier properties for gases.Herein, so-called phase separation refers to：What is coexisted under compatible state is of more than two kinds different from each otherIngredient is separated into the phase to be respectively principal component.In addition, so-called phase separation structure refers to the structure formed by phase separation.
The presence or absence of phase separation structure can be confirmed by micro- sem observation.When confirming phase separation structure, it can correspond toIn its structural cycle, it is separated and is tied by observations such as light microscope, scanning electron microscope, transmission electron microscopesStructure.
The preferred phase separation structure of sheet material of the present invention is any one of co-continuous structure or island structure.If phase separationStructure is co-continuous structure or island structure, then easily controllable into desired structural cycle, becomes easy when forming inorganic layerIn the structure of control inorganic layer, the inorganic matter laminate film of readily available high gas-obstructing character.
So-called co-continuous structure herein refers to that each phase of more than two kinds of separation forms the continuous phase of three-dimensional complexing each otherStructure.The ideograph of the co-continuous structure is for example documented in " polymer alloy basis is with applying (second edition) (the 10.1st chapter) "(polymer science can be compiled：The same people of Tokyo chemistry) (mono- ァ ロ イ Ji Foundation と ying (second edition) (the 10.1st chapter) (polymer sciences of Port リ マIt can compile：The same people of beam capital chemistry)).In addition, so-called island structure refers to following structures：Ingredient there are a side is the shape of principal componentAs the matrix of the part of particle shape and the ingredient of the opposing party for principal component, the ingredient of a side is with particle shape point in the matrixIt dissipates and exists.It should be noted that lamellar phase structure can also be formed in the present invention other than co-continuous structure, island structureThe phase separation structures such as (with reference to Fig. 8), Gyroid phase structures (with reference to Fig. 7), column phase structure (with reference to Fig. 6).
Herein, so-called lamellar phase structure refers to form the phase separation structure of 2 phases of layer structure stacking.It is in addition, so-calledGyroid phase structures, referring to the branch of the bifurcated in the phase separation structure comprising 2 phases becomes the co-cable transmission separated structure of 3.In addition, so-called column phase structure, refer to that 1 phase in 2 phases forms club shaped structure, these club shaped structures at least partially, it is equidirectionalThe phase separation structure being regularly configured.
Herein, the structural cycle of co-continuous structure or island structure can be confirmed by micro- sem observation.Structure weekWhen phase is 0.1 μm~100 μm, it can be confirmed by light microscope.In addition, structural cycle for 0.001 μm less than 0.1μm when, transmission electron microscope or scanning electron microscope can be passed through and confirmed.
During confirmation, by obtaining the MIcrosope image of observation multiplying power mutually fitted with the structural cycle envisioned, knot can be confirmedThe structure period.Such as the structural cycle of anticipation is observed for 0.001 μm less than at 0.1 μm with 50,000 times, is 0.1 μmIt is observed, is observed when being 1 μm or more with 100 times, thus, it is possible to according to gained with 5,000 times less than at 1 μmMIcrosope image confirm structural cycle.
The sheet material of the present invention is preferably the polymer alloy containing at least two kinds of resin components.If sheet material is contains at least 2The polymer alloy of kind resin component, then be easily formed phase separation structure, when forming inorganic layer, easily controllable inorganic layerStructure is easy to improve barrier properties for gases.
Herein, so-called polymer alloy refers to include the macromolecule multicomponent system of at least two kinds of resin components.Polymer closesAs long as the ingredient of gold forms the combination of phase separation structure, there is no particular limitation, and organic family macromolecule or inorganic are highMolecule is applicable.The dispersed structure of the sheet material of the present invention is phase separation structure, when being co-continuous structure or island structure, preferablyAt least two kinds of resin components form phase separation structure by spinodal decomposition.Phase separation structure, energy are formed by using spinodal decompositionEnough easily control is desired structure size, when forming inorganic layer, becomes prone to the structure of control inorganic layer, is easy toObtain the inorganic matter laminate film of high gas-obstructing character.
Herein, it is so-called using spinodal decomposition formed phase separation structure, refer to for 2 different ingredients resin composition andIn the phasor of temperature, formed by the phase separation of the unstable state generation in the inside of spinodal (Spinodal curve)Structure.So-called spinodal is herein：It is the phase in the resin for mixing 2 different ingredients for the curve that composition and temperature are drawn inThe difference (Δ Gmix) of total free energy of free energy and 2 incompatible phases during appearance uses concentrationIt carries out obtained by second order partial differentialThe value arrivedFor 0 curve, in addition in the inside of spinodal, it isUnstable state, on the outside for
Based on detailed theory, in spinodal decomposition, in the temperature equably compatible mixed system of compatibility areaTemperature when the temperature for sharp becoming unstable region, system start to coexist composition be rapidly separated.At this timeConcentration is mutually complexed continuously and regularly jointly under certain wavelength by monochromatization, two separation of formation with structural cycle (Λ m)Co-continuous structure, therefore, suitable for the above-mentioned formation with fine and homogeneous texture phase separation structure.It will be as described aboveGround form co-continuous structure after, only increase in a state that its structural cycle keeps certain two-phase concentration difference process, referred to asThe preliminary process of spinodal decomposition.The preliminary process of the spinodal decomposition can be by being confirmed via following process, that is, is dissipated in lightIt penetrates, X ray is scattered in measure etc., the intensity increase of the scattering peak from periodic structure but Scattering of Vector corresponding with its maximum valueThe value of (scattering vector) is constant.
In spinodal decomposition, after above-mentioned preliminary process, via mid-term process (while generation wavelength increase and concentration difference increaseGreatly), after concentration difference reaches and the composition stage coexists, via late stage (wavelength increase with self-similar manner is generated), finally intoIt goes to 2 phases for being separated into macroscopic view.During the wavelength increase from mid-term process to late stage, due to composition, interfacial tensionInfluence, the continuity there is also the phase of a side blocks, becomes from above-mentioned co-continuous structure the situation of island structure.
As inorganic family macromolecule, oxide of inorganic etc. can be enumerated, can use and be passed through by following Si oxidesMacromolecule obtained by hydrolytic-polymeric reaction, the Si oxide, for example, tetramethoxy-silicane, tetraethoxysilane, four are justTetraalkoxysilanes class, methyltrimethoxysilane, the first such as npropoxysilane, tetraisopropoxysilan, four n-butoxy silanesEthyl triethoxy silicane alkane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl trimethoxy silane, n-propyl threeEthoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, n-butyltrimethoxysilane, normal-butyl threeEthoxysilane, n-pentyl trimethoxy silane, n-pentyl triethoxysilane, n-hexyl trimethoxy silane, n-heptyl threeMethoxy silane, n-octyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyl threeMethoxy silane, cyclohexyltriethyloxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3- chloropropyl front threesOxysilane, 3- chloropropyl triethoxysilanes, 3,3,3- trifluoro propyl trimethoxy silanes, 3,3,3- trifluoro propyl, three ethoxyBase silane, 2- hydroxyethyls trimethoxy silane, 2- hydroxyethyls triethoxysilane, 2- hydroxypropyls trimethoxy silane,2- hydroxypropyls triethoxysilane, 3- hydroxypropyls trimethoxy silane, 3- hydroxypropyls triethoxysilane, 3- epoxies thirdOxygroup propyl trimethoxy silicane, 3- glycidoxypropyl groups triethoxysilane, 2- (3,4- expoxycyclohexyl) ethyl threeMethoxy silane, 2- (3,4- expoxycyclohexyl) ethyl triethoxysilane, 3- (methyl) acryloxypropyl trimethoxyBase silane, 3- (methyl) acryloxypropyls triethoxysilane, vinyltrimethoxysilane, vinyl triethoxyl siliconThe trialkoxysilanes such as alkane, allyltrimethoxysilanis, vinyltriacetoxy silane, methyl triacetoxysilaneOrganoalkoxysilanes such as (methyltriacetyl oxysilane), methyl triple phenoxyl silane etc..
As organic family macromolecule, thermoplastic resin, thermosetting resin, light-cured resin etc. can be enumerated, such as canTo enumerate polyester resin, polycarbonate resin, acrylic resin, methacrylic resin, polyurethane based resin, polyethersPolyamide-based resins, ABS resin, polyimide based resin, the poly- second such as resinoid, polycyclic oxygroup resinoid, nylon, benzoguanamineThe olefine kind resins such as alkene, polypropylene, polystyrene resin, vinylite, melamine resinoid, phenolic treeThe resin containing chlorine element (Cl elements) such as fat, polyvinyl chloride, polyvinylidene chloride, has the resin containing fluorine element (F elements)Machine silicon resinoid, cellulosic resin, etc. organics high-molecular compound, can be with based on required characteristic, productivity etc.It is at least one kind of from wherein selecting, alternatively, it is also possible to which two or more in them is mixed, but preferably comprised in the sheet material of the present inventionCrosslinking components more than 2 functions.
By that can be easily desired structure by phase separation structure control containing crosslinking components more than 2 functionsSize when particularly forming inorganic layer, can easily control the structure of inorganic layer, obtain the inorganic of high gas-obstructing characterObject laminate film.
Crosslinking component more than above-mentioned 2 function can be obtained by the way that following compounds are carried out polymerisation (cross-linking reaction)It arrives, the compound includes the monomer with the reactive functional groups for contributing to polymerisation of 2 or more, oligomer, polymerizationObject.
As reactive functional groups, for example, isopropenyl, isopentene group, pi-allyl, acryloyl group, methyl-propEnoyl- (methacryloyl group), acryloxy, methacryloxy, methylacryloyl (methacryl),Acrylamido, methacryl amido, allylidene (allylidene group), secondary pi-allyl (allylidyneGroup), vinyl ether group；Group that bond with carbon on the halogen elements such as fluorine, chlorine and carbon-to-carbon double bond forms (for example, fluoride-based,Vinylidene fluoride, chlorovinyl, polyvinylidene chloride etc.)；Phenyl, naphthalene etc. have on the substituent group and carbon-to-carbon double bond of aromatic ringsThe group (such as styryl etc.) that forms of bond with carbon；Butadienyl is (for example, CH2=C (R1)-C(R2)=CH-, CH2=C(R1)-C (=CH2)-(R1、R2For H or CH3)) such group with conjugated polyene structure；Hydroxyl, carbonyl, phosphate, ammoniaBase, quaternary ammonium salt base, sulfonic group, cyano isopolarity group；And a part for these polar groups has Na+、K+Etc. contend with sun fromThe state of son is (for example,-ONa ,-COONa ,-SO3Na etc.) polar group；Its containing heterocycle such as Nei Zhi oxazoles imidazolesHis aromatic group and its open loop group；The sulfur-bearings such as epoxy group (also comprising glycidyl), isocyanate group, sulfydryl sulfenylThe functional group of element；Functional groups of Nitrogen elements such as urea groups ketimide base (ketimino) etc..It is contemplated that required spyProperty, productivity etc., using a kind therein or are mixed with two or more.
As the compound for the reactive functional groups for contributing to polymerisation with 2 or more, for example, season pentaTetrol triacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetraacrylate, pentaerythrite tetramethyl acrylic acidEster, pentaerythrite ethoxy triacrylate, pentaerythrite ethyoxyl trimethyl acrylic ester, pentaerythrite ethyoxyl tetrapropyleneAcid esters, pentaerythrite ethyoxyl tetramethyl acrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate acidEster, dipentaerythritol tetraacrylate, dipentaerythritol tetramethyl acrylate, Dipentaerythritol Pentaacrylate, two seasons pentaTetrol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, trimethylolpropaneTriacrylate, trimethylol-propane trimethacrylate, trimethylolpropane ethoxy triacrylate, trihydroxy methyl thirdAlkane ethyoxyl trimethyl acrylic ester, double trimethylolpropane triacrylate, double trimethylolpropane trimethyl acrylic ester,It is double trimethylolpropane tetraacrylate, double trimethylolpropane tetramethyl acrylate, glycerine propoxylate, sweetThe intramolecular of oily propoxyl group trimethyl acrylic ester, cyclopropane ring, ring fourth ring, penta ring of ring, hexamethylene ring etc. has cyclic skeletonCompound is (for example, five acrylic acid of triacrylate trimethyl acrylic ester tetraacrylate tetramethyl acrylateSix acrylate hexamethacrylate of ester pentamethacrylate etc.)；By a part of modified of these compoundsThe compound arrived (such as is modified pentaerythritol triacrylate, 2- hydroxyls with the modified 2- hydroxy propanes acid such as 2- hydroxy propane acidBase propane acid is modified pentaerythritol acrylate trimethyl, 2- hydroxy propanes acid is modified pentaerythritol tetraacrylate, 2- hydroxylsPropane acid is modified pentaerythritol tetramethylacrylate, in addition, having imported the organosilicon triacrylate of silicone backbone, organicIt is silicon trimethyl acrylic ester, organosilicon tetraacrylate, organosilicon tetramethyl acrylate, five acrylate of organosilicon, organicSilicon pentamethacrylate, six acrylate of organosilicon, organosilicon hexamethacrylate etc.)；There is vinyl in skeletonAnd/or compound while ethenylidene also with other skeletons is (for example, the carbamate with carbamate skeletonTriacrylate, carbamate trimethyl acrylic ester, urethane tetraacrylates, carbamate tetramethyl propyleneAcid esters, five acrylate of carbamate, carbamate pentamethacrylate, six acrylate of carbamate, aminoFormic acid esters hexamethacrylate, polyethers triacrylate, polyethers trimethyl acrylic ester, the polyethers tetrapropylene with ether skeletonAcid esters, polyethers tetramethyl acrylate, five acrylate of polyethers, polyethers pentamethacrylate, six acrylate of polyethers, polyethersHexamethacrylate, epoxy group triacrylate, epoxy group trimethyl acrylic ester, the ring with the skeleton from epoxy groupOxygroup tetraacrylate, epoxy group tetramethyl acrylate, five acrylate of epoxy group, epoxy group pentamethacrylate, ringSix acrylate of oxygroup, epoxy group hexamethacrylate, polyester triacrylate, the polyester trimethacrylate with ester skeletonAcid esters, polyester tetra acrylate, polyester tetramethyl acrylate, five acrylate of polyester, polyester pentamethacrylate, polyesterSix acrylate, polyester hexamethacrylate etc.), but it's not limited to that.
In the present invention, in sheet material (for single layer structure sheet material, that is, sheet material (i) in the case of in sheet material (i) itself, beIn the case of sheet material, that is, sheet material (ii) of laminate structures in base material and/or substrate layer), it can be in the effect for not damaging the present inventionIn the range of add various additives.As additive, such as organic and inorganic particle can be used, fire retardant, fire-retardant helpedAgent, heat-resisting stabilizing agent, antioxidative stabilizer, even paint, slip agent, antistatic agent, ultra-violet absorber, Photostabilised dose, intoCore agent, dyestuff, filler, dispersant and coupling agent etc..
To be formed with substrate layer in the face of at least one party of base material, (it is 0.001 μ with structural cycle to the sheet material of the present inventionThe dispersed structure of m~100 μm) sheet material (ii) when, as used base material at this time, specifically for example, treeFat, glass etc..
As the resin for base material, polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid ethylene glycol can be enumeratedThe polyenes such as the polyester such as ester (PEN), polyamide, polyimides, polyphenylene sulfide, aromatic polyamides, polyethylene (PE), polypropylene (PP)The acrylic compounds first such as hydrocarbon, polyvinyl alcohol, polystyrene, polylactic acid, polyvinyl chloride, makrolon, polymethyl methacrylateBase acrylic resin, ester ring type acrylic resin, cyclic olefin resins (COP), cycloolefin copolymer resin (COC), triacetylCellulose (TAC), ABS, polyvinyl acetate, melamine resinoid, phenolic resinoid, polyvinyl chloride, polyvinylidene chlorideDeng resin, the resin containing fluorine element (F elements), organic silicon resin, ethylene vinyl acetate containing chlorine element (Cl elements)Saponified (the saponification products) of ester copolymer, polyacrylonitrile, polyacetals etc..
In addition, above-mentioned resin can be homopolymer, copolymer, that is to say, that either individual polymer, it can alsoIt is that multiple polymers blending is used, mixed and/or be copolymerized obtained substance.In addition, common sodium can be used as glassGlass.
Furthermore, it is also possible to their multiple combinations are used.For example, can by resin and glass combination, can also beThe compound resin that two or more laminated resin forms.
For the thickness of base material, it can be less than 250 μm (base material can be wound), thickness can also be made to be more than 250 μm.From the viewpoints such as cost, productivity, operability consider, preferably 250 μm hereinafter, more preferably 150 μm hereinafter, and then preferably100 μm hereinafter, particularly preferably less than 50 μm.In addition, the lower limit of the thickness of base material is not particularly limited, but strong from ensuring to stretchFrom the viewpoint of degree, impact strength, more preferably 5 μm or more, and then preferably 10 μm or more.
In the case where the film for using above-mentioned resin is as base material, it can be applicable in and resin not stretched and manufacturedResin is carried out uniaxial stretching, biaxial stretch-formed and manufactured film by film.Furthermore, it is also possible to using monofilm or 2 layers or more,Such as the film formed is film-made by coetrusion, stretches film formed etc. along uniaxial direction or biaxially oriented.
There is the surface of substrate layer side in the formation of base material, in order to make adaptation excellent, it is possible to implement following pre-treatments：CoronaProcessing, ion bombardment processing, solvent processing, roughening treatment and formed tackifier coating (its by organic matter or inorganic matter or itMixture form) processing.In addition, in order to improve lubricity during winding and in order to mitigate after inorganic layer is formedFriction when being wound between inorganic layer can grant organic matter, inorganic matter in the opposing face for forming inorganic layer sideOr the coating layer of their mixture.
In these base materials, consider that it is preferable to use poly- from viewpoints such as the optical characteristics such as mouldability, the transparency, productivitiesThe polyester films such as ethylene glycol terephthalate, polyethylene naphthalate, in addition it is also preferred that using with poly- naphthalenedicarboxylic acid second twoAlcohol ester mixes and/or the polyethylene terephthalate film of copolymerization, polypropylene screen, cycloolefin resin film, cycloolefin copolymer treeAdipose membrane.
Formed the present invention sheet material method (to be the forming method of sheet material (i) during single layer structure sheet material, that is, sheet material (i),To be the method that substrate layer is formed on base material during laminate structures sheet material, that is, sheet material (ii)) it is not particularly limited, but preferably includeFollowing process：The ingredient for forming sheet material (i) and the ingredient for forming substrate layer respectively form sheet material (i) and during substrate layer viaCompatible state forms phase separation structure.It should be noted that herein, so-called compatible state refer to contained at least two kinds of resins intoDivide the state equably mixed with molecular level, specifically, referring to that the phase containing 2 kinds of different resin components is not formedThe situation of 0.001 μm or more of phase separation structure.By the way that comprising above-mentioned operation, easily phase separation structure can be controlled as instituteDesired structure size, when forming inorganic layer the structure of easily controllable inorganic layer, obtain the inorganic of high gas-obstructing characterObject laminate film.
As the method comprising above-mentioned operation, for example, when being sheet material (i), following method can be enumerated：Will contain sheet material intoThe blend compositions divided pass through heat fusing molding etc. and form phase separation structure；During for sheet material (ii), following method can be enumerated：In the formation of substrate layer, prepare and include the coating fluid of substrate layer composition, using casting, spin-coating method, Dipcoat method, stick coating method,Spray coating method, scraper for coating method, slot-form die rubbing method, gravure coating process, inverse coating, silk-screen printing, casting mold coating, printing turnThe common methods such as the wet coating methods such as print, ink-jet application are coated on base material, later, the ingredient of substrate layer are made using following methodsPolymerization forms the phase separation structure of substrate layer.It is excellent in the case of for sheet material (ii) in the above-mentioned coating method for forming substrate layerChoosing can equably and productivity forms substrate layer well, the wet coating that is coated with using micro gravure or slot-form dieMethod.
In addition, in order to make the ingredient of the ingredient of sheet material (i) and substrate layer equably compatible, it can also be when for sheet material (i)The blend compositions (hereinafter, also be sometimes referred to simply as blend compositions) containing sheet material (i) ingredient and containing during for sheet material (ii)There is mixed solvent in the coating fluid (hereinafter, being also sometimes referred to simply as coating fluid) of substrate layer composition.Use the mixing for being mixed with solventWhen composition and coating fluid, after being coated using the above method, maintaining the ingredient of sheet material (i) and forming the ingredient of substrate layerCompatible state in the case of after it can make it dry the temperature that solvent volatilizees, when can be with without solvent identically, makeThe ingredient polymerization of the ingredient and substrate layer of sheet material (i) forms the phase separation structure of sheet material (i) and substrate layer.
For solvent used in the above situation, as long as it is compatible with the ingredient of sheet material (i) and the ingredient of substrate layerSolvent, be not particularly limited, can be based on sheet material (i) ingredient and the ingredient of substrate layer, the type of forming method andAppropriate selection, for example, the acetate esters such as ethyl acetate, butyl acetate, acetone, acetophenone, ethyl methyl ketone, methylThe ketones such as isobutyl ketone, toluene, dimethylbenzene, benzyl alcohol etc. are aromatic hydrocarbon, methanol, ethyl alcohol, 1,2-PD, terpinol, secondIt is sour pine tar ester (acetyl terpineol), butyl carbitol, ethyl cellosolve, ethylene glycol, triethylene glycol, tetraethylene glycol, sweetEthylene glycol monoalkyl ethers class, glycol dialkyl ether class, the diethylene glycol monoalky lethers such as the alcohols such as oil, triethylene glycol monobutyl base etherAcetate esters, ethylene glycol list aryl ethers, polyethyleneglycol aryl ethers, propylene-glycol monoalky lether class, dipropylene glycol dialkyl groupEthers, propylene-glycol monoalky lether acetate esters, ethylene carbonate, propylene carbonate, gamma-butyrolacton, solvent naphtha, water, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide, dimethyl ethylene urea, N, N '-dimethyl propylidene urea,Tetramethylurea etc. can also contain two or more above-mentioned solvent.
As the curing for the phase separation structure for being used to form sheet material (i) and substrate layer, can enumerate through heating etc.From the external method for applying energy, it is preferable to use the method that electromagnetic wave or the particle beams form phase separation structure.By using electromagnetismWave or the particle beams, just via the compatible state of the ingredient of above-mentioned composition sheet material (i) and the ingredient for forming substrate layer, formation phase pointFor the process of structure, become easily to carry out, be desired structure size so as to be easy to phase separation structure control, thusWhen forming inorganic layer, the structure of control inorganic layer is become prone to, the inorganic matter of readily available high gas-obstructing character is laminatedSheet material.
As electromagnetic wave, gamma-rays, X ray, ultraviolet light, visible ray, infrared ray, microwave etc. can be enumerated, additionally asThe particle beams can enumerate α lines, β lines, electric wire, proton beam, neutron beam etc., can be according to the ingredient and composition for forming sheet material (i)Type, the property of the ingredient of substrate layer combine two or more in them, in order to make under the action of electromagnetic wave or the particle beamsThe ingredient for forming sheet material (i) and the ingredient for forming substrate layer carry out polymerisation curing reaction, preferably comprise initiator.
Herein, so-called initiator is under the action of electromagnetic wave or the particle beams, and generation makes the reactive species that reaction proceeds byThat is free radical kind, cation kind, anion kind isoreactivity kind, so as to the substance for proceeding by chemical reaction.Drawn by containingAgent is sent out, electromagnetic wave or the particle beams are irradiated to it, it is anti-for polymerisation curing so as to which system is made integrally to simultaneously createThe initiation kind answered, therefore initiation can be shortened and cure required time, hardening time, just via above-mentioned composition sheet material (i)Ingredient and form substrate layer ingredient compatible state, formed phase separation structure process for, become prone to carry out, so as toIt is easy to control phase separation structure in desired structure size, as a result, when forming inorganic layer, becomes prone to control inorganicThe structure of nitride layer, the inorganic matter laminate film of readily available high gas-obstructing character.
As workable initiator, for example, benzophenone, dihydroxy benaophenonel, 4- phenyl benzophenones etc.The benzoin class such as benzophenone, benzoin dimethyl ketal, 1- hydroxy-cyclohexyl-phenyls-ketone, 2- hydroxy-2-methyls-1- phenyl -1- acetone, 2- methyl 1 [4- (methylsulfany) phenyl] -2- morpholinyl -1- acetone, 2- benzyl -2- dimethylaminos -Alpha-hydroxies ketone, alpha-amido ketone, isopropyl thioxanthone, the 2-4- diethyl thioxanthones such as 1- (4- morpholino phenyls) -1- butanoneEtc. thioxanthene ketone class, phenylglyoxalates methyl esters (methyl phenyl glyoxylate) etc., value, extinction from maximum absorption wavelengthThe viewpoints such as degree, color, coloring degree consider, can use a kind in above-mentioned initiator or two or more is applied in combination.
For above-mentioned Photoepolymerizationinitiater initiater, as commercially available product, it can be lifted as 1- hydroxy-cyclohexyl-phenyls-ketoneGo out IRGACURE 184 (BASF AG's system), can be with as 2- methyl 1 [4- (methylsulfany) phenyl] -2- morpholinyl -1- acetoneEnumerate IRGACURE 907 (BASF AG's system), as 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) -1- butanoneCan enumerate IRGACURE 369 (BASF AG's system) etc., type, the property of the ingredient based on sheet material, can only containing a kind orContain different two or more of absorbing wavelength region.
In addition, the condition (output condition etc.) of the irradiation bodies such as the lamp of electromagnetic wave or the particle beams is irradiated by change, changes and shinesIrradiation distance between beam and non-irradiated body and removing by adjusting the manufacture required non-irradiated body of sheet material of the inventionRunning speed degree come shorten irradiation time, the methods of, for control to adjust cumulative exposure be also effective, and then, irradiation electricityWhen magnetic wave or the particle beams, in the atmosphere replaced with non-active gas such as nitrogen, argon gas, the atmosphere for eliminating oxygen etc.The method of the low specific atmosphere of oxygen concentration be also it is effective, therefore, can be by the way that they be appropriately combined to form sheet material.
The thickness of substrate layer during for sheet material (ii), preferably more than 50nm, less than 10 μm.If thinner than 50nm, byTo the concave-convex influence of base material, the inorganic matter laminate film of high gas-obstructing character cannot be obtained sometimes.If than 10 μ m-thicks, serve as a contrastThe stress of bottom becomes larger, and leads to substrate camber, is cracked in inorganic layer, therefore, similarly, the presence of cannot obtain high gasThe situation of the inorganic matter laminate film of body barrier property.It should be noted that the thickness of substrate layer can be by passing through transmission electronThe cross-section image that microscope (TEM), scanning electron microscope (SEM) obtain is measured.
[inorganic layer]
For the inorganic matter laminate film of the present invention, the structure of inorganic layer is controlled using sheet material, is thus shownHigh gas-obstructing character.It should be noted that multi-layer laminate structure can also be formed (that is, after inorganic layer is formed furtherStructure obtained from laminated substrate layer and inorganic layer repeatedly).In addition, inorganic layer can be only configured in the unilateral side of sheet material, onlyWhen one-sided configuration, whens the stress equilibrium that there is a situation where inorganic layer side and opposite side is destroyed generation warpage, deformation etc.,Can inorganic layer be set on the two sides of sheet material.The inorganic matter laminate film of the present invention particularly preferably has 40 DEG C of temperature, humidityMoisture-vapor transmission during 90%RH is 1g/ (m2Atm for 24 hours) following barrier properties for gases.
The thickness of inorganic layer in the present invention is preferably more than 10nm, more preferably more than 50nm.If inorganic layerThickness ratio 10nm it is thin, then the position of barrier properties for gases cannot be substantially ensured by generating sometimes, in the face of inorganic matter laminate filmIt is unequal to generate barrier properties for gases.In addition, the upper limit of the thickness of inorganic layer in the present invention is preferably 2,000nm hereinafter, morePreferably below 1,000nm.If the thickness ratio 2 of inorganic layer, 000nm is thick, then remaining stress becomes larger in film, therefore, hasWhen be easy to crack in inorganic layer in bending, under the action of external impact, along with using, barrier properties for gases dropIt is low.
Form inorganic layer inorganic compound be not particularly limited, can be only inorganic matter, or organic matter withThe mixture of inorganic matter, from being easy to show the effect as caused by the sheet material of the present invention, particularly be easy to show raising gasFrom the aspect of the effect of body barrier property, the list of the element of 1~17 race in 2~6 periods for belonging to the periodic table of elements is preferably comprisedMatter or at least one kind of element.As the specific element contained by inorganic layer, for example, silicon (Si), aluminium (A1), zinc(Zn), titanium (Ti), zirconium (Zr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta), palladium (Pd) etc..Above-mentioned element can be withThe form of simple substance is included in the form of the compounds such as carbide, oxide, nitride, sulfide or their mixtureIn inorganic layer.
As an example of the element contained by inorganic layer, illustrated for silicon (Si).As the compound of silicon, Ke YijuGo out silica (SiO2) etc. Si oxides, silicon nitride (Si3N4) etc. silicon nitrides, preferably Si oxide.
For the composition of Si oxide, it is 1.5~2.0 to preferably comprise oxygen atom relative to the atomicity ratio of silicon atomSi oxide.If oxygen atom is more than 2.0 relative to the atomicity ratio of silicon atom, contained oxygen atom quantitative change is more, thereforeSometimes gap section, defect part increase, and the improvement effect of the barrier properties for gases of the inorganic matter laminate film of gained is small.In addition,If oxygen atom is less than 1.5 relative to the atomicity ratio of silicon atom, oxygen atom is reduced, and forms fine and close film quality, but flexibilityIt reduces, is easy to crack in heat, under the action of external stress sometimes.Oxygen atom relative to silicon atom atomicity ratioMore preferably ranging from 1.7~1.9.
It should be noted that for the composition analysis of silicon compound, can X-ray photoelectron spectroscopy be used according to composition(XPS methods), ICP emission spectroanalysis and rutherford back scattering analysis (Rutherford backscatteringAnalysis), quantitative analysis is carried out to the containing ratio of the atom of each element, be thus obtained.It is also laminated on inorganic layer to have treeDuring lipid layer, carried out after by ion-etching or liquid processing, its caliper portion being obtained using X ray reflection rate method is removedAnalysis.
The method for forming the inorganic layer containing silicon compound is not particularly limited, such as passes through vacuum vapour deposition, sputteringMethod, ion plating method, chemical vapour deposition technique (referred to as CVD method) and use the above-mentioned wet of the coating fluid containing silicon compoundThe formation such as formula rubbing method.During using vacuum vapour deposition, preferred following methods：Vapor deposition contains atom in the environment of further decompressionThe small element of radius and low-melting evaporation material is so as to form inorganic layer.It is thin due to being formed in the case of using sputtering methodThe diffusion into the surface of the particle of film and the film for forming fine and close film quality, it is therefore preferable that using plasma assists sputtering method, that is,Other than the plasma of sputtering target material, on the surface of sheet material on one side with oxygen, carbon dioxide isoreactivity gasPlasma carries out auxiliary and forms film on one side.During using CVD method, preferably by the plasma of high intensity by silicon class compoundMonomer gas activation, fine and close silicon based thin film layer is formed by polymerisation.In these methods, more preferable sputtering method or CVDMethod.
As the silicon class compound suitable for CVD method, for example, silane, methyl-monosilane, dimethylsilane, front threeBase silane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethyl silane, npropoxysilane, dipropyl oxygenBase silane, tripropoxy silane, tetrapropoxysilane, dimethyldisiloxane, tetramethoxy-silicane, tetraethoxysilane, fourNpropoxysilane, tetramethyl disiloxane, hexamethyldisiloxane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxy-silicaneAlkane, hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten monomethyl rings, six siloxanes, diformazanBase disilazane, trimethyldisilazane, tetramethyl-disilazane, hexamethyldisilazane, hexamethyl cyclotrisilazane, eight firstBase cyclotetrasilazane, five silazane of decamethyl ring, ten monomethyl rings, six silazane etc..Wherein, it is excellent from the viewpoint of operabilitySelect hexamethyldisiloxane, tetraethoxysilane.
Next, other examples as the element contained by inorganic layer, illustrate for zinc (Zn).As zinc compoundZinc oxide (ZnO), zinc sulphide (ZnS) etc. can be enumerated.Zinc compound is preferably 50 matter of inorganic layer entirety in the present inventionMeasure more than %, more preferably more than 60 mass %, and then preferably more than 80 mass %.
It should be noted that zinc compound is handled in the form of the compound with following composition formulas herein, it is describedIn round figures, and each element passes through following X-ray photoelectron spectroscopies (XPS methods), ICP to the ratio of components of each element in composition formulaEmission spectroanalysis, Rutherford backscattering method etc. determine ingredient.Such as even if condition during due to generation is different,ZnS, ZnO are still handled in the form of ZnS, ZnO when becoming with metering than slightly ratio of components devious, calculate above-mentioned matterMeasure containing ratio.
Formed the inorganic layer containing zinc compound method be not particularly limited, such as can by vacuum vapour deposition,The formation such as sputtering method, ion plating method, CVD method.In these methods, as the method for can be easy and inexpensively being formed, preferably sputterMethod.
As long as the inorganic layer containing zinc compound contains zinc, it can also further contain silicon (Si), aluminium (Al), titanium(Ti), the simple substance of other elements such as zirconium (Zr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta), palladium (Pd) or carbonizationThe compounds such as object, oxide, nitride, sulfide can contain one or more in them, of the invention inorganic compoundsThe compound formed preferably by the composition containing zinc compound and Si oxide, can obtain barrier properties for gases more at this timeHigh inorganic matter laminate film.For example, as the layer that can obtain high gas-obstructing character, it is preferable to use containing zinc oxide-dioxyThe layer (hereinafter referred to as [inorganic A] layer) of the coexisting phase of SiClx-aluminium oxide or the coexisting phase containing zinc sulphide and silicaLayer (hereinafter referred to as [inorganic B] layer).(it should be noted that hereinafter detailed for [inorganic A] layer and [inorganic B] layer differenceGround illustrates).
[the layer of the coexisting phase containing zinc oxide-silicon dioxide-aluminium oxide：It is A layers inorganic]
For the layer of the coexisting phase containing zinc oxide-silicon dioxide-aluminium oxide for the inorganic layer for being preferably used as the present invention([inorganic A] layer) illustrates.It should be noted that also " coexisting phase of zinc oxide-silicon dioxide-aluminium oxide " is abbreviated sometimesFor " ZnO-SiO2-Al2O3”.In addition, for silica (SiO2) for, based on the difference of condition when generating, generate sometimesWith the silicon of above-mentioned composition formula and the composition ratio of oxygen substance (SiO~SiO slightly devious2), but represent in the present specificationFor silica or SiO2, formed and handled with this.About and the ratio of components chemical formula generate deviation, zinc oxide,Aluminium oxide is also using same processing mode, in the present specification, regardless of the inclined of the ratio of components caused by condition when generatingHow is difference, is respectively denoted as zinc oxide or ZnO, aluminium oxide or Al2O3, handled with above-mentioned form.
For by making the good original of barrier properties for gases using [inorganic A] layer in the inorganic matter laminate film of the present inventionCause, thus it is speculated that be due to：Make the crystallised component and titanium dioxide contained by zinc oxide in the coexisting phase of zinc oxide-silicon dioxide-aluminium oxideThe amorphous component of silicon coexists, and thus tends to generation crystallite, and the crystalline growth of zinc oxide is suppressed, and grain size becomes smaller, therefore layer is fine and closeChange, inhibit the transmission of oxygen and vapor.
It is compared additionally, it is believed that there being zinc oxide together with the situation of silica, it, can be into one by the way that aluminium oxide has coexistedStep inhibits crystalline growth, therefore the barrier properties for gases caused by crackle generates can be inhibited to reduce.
As follows, the composition of [inorganic A] layer can be measured by ICP emission spectroanalysis method.It is preferred that it is shone by ICPThe Zn atomic concentrations that spectra methods measures are 20~40atom%, Si atomic concentrations are 5~20atom%, Al atomic concentrations areA concentration of 35~70atom% of 0.5~5atom%, O atom.
If Zn atomic concentrations are more than 40atom% or Si atomic concentrations and are less than 5atom%, zinc oxide is inhibited to crystallize intoLong oxide is insufficient, therefore gap section, defect part increase sometimes, it is impossible to obtain sufficient barrier properties for gases.IfZn atomic concentrations are less than the amorphous component for the silica that 20atom% or Si atomic concentrations are more than inside 20atom%, then layerIncrease, the flexibility of layer reduces, and is easy to crack in heat, under the action of external stress sometimes.In addition, if Al is formerSub- concentration is more than 5atom%, then the compatibility of zinc oxide and silica exceedingly increases, therefore sometimes in heat, from outsideStress under the action of be easy to crack.If Al atomic concentrations are less than the parent of 0.5atom%, zinc oxide and silicaIt is become inadequate with property, cambial interparticle binding force can not improve, therefore flexibility reduces, sometimes in heat, from outerIt is easy to crack under the action of the stress in portion.In addition, if O atom concentration were more than 70atom%, would lacking in [inorganic A] layerThe amount of falling into increases, therefore cannot obtain defined barrier properties for gases sometimes.If O atom concentration be less than 35atom%, zinc, silicon,The state of oxidation of aluminium becomes inadequate, it is impossible to inhibit crystalline growth, and grain size becomes larger, therefore barrier properties for gases reduces sometimes.FromAbove-mentioned viewpoint considers that more preferable Zn atomic concentrations are 25~35atom%, Si atomic concentrations are 10~15atom%, Al atoms are denseIt spends for 1~3atom%, a concentration of 50~64atom% of O atom.
For the ingredient contained by [inorganic A] layer, as long as zinc oxide, silica and aluminium oxide are above-mentioned compositing rangeAnd be main component, it is not particularly limited, can further contain such as silicon (Si), aluminium (Al), zinc (Zn), titanium (Ti), zirconium(Zr), the simple substance of other elements or carbide, the oxidation such as tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta), palladium (Pd)The compounds such as object, nitride, sulfide, can be containing one or more in them.So-called main component refers to for [nothing hereinMachine A] layer composition more than 50 mass %, preferably more than 60 mass %, more preferably more than 80 mass %.
For the composition of [inorganic A] layer, by with mixed sintering material used during forming layer it is equal form shapeInto therefore, by using corresponding with the composition of destination layer mixed sintering material is formed, the composition of [inorganic A] layer can be adjusted.
For the composition analysis of [inorganic A] layer, using ICP emission spectroanalysis method, zinc, silicon, aluminium each element are determinedAmount analysis can know the ratio of components of zinc oxide, silica, aluminium oxide and the inorganic oxide contained.It should be noted thatFor oxygen atom, zinc atom, silicon atom, aluminium atom are assumed that respectively with zinc oxide (ZnO), silica (SiO2), oxygenChange aluminium (Al2O3) form exist and calculate.
ICP emission spectroanalysis, be can by luminescent spectrum (when sample to import together with argon gas to plasma source portion andGenerate) while the analysis method of multielement is measured, it can be suitably used for composition analysis.On inorganic layer it is laminated have resin layer when,After removing the caliper portion being obtained using X ray reflection rate method by ion(ic) etching, liquid processing, ICP luminescent spectrums point are carried outAnalysis.
The method that [inorganic A] layer is formed on sheet material (i) and on the substrate layer of sheet material (ii) is not particularly limited, can be withUsing the mixed sintering material of zinc oxide, silica and aluminium oxide, pass through the shapes such as vacuum vapour deposition, sputtering method, ion plating methodInto.Using zinc oxide, silica and aluminium oxide monomer material when, zinc oxide, silica and aluminium oxide can be distinguishedIt is deposited or sputtered simultaneously by different evaporation source or sputtering electrode, carrying out mixing makes it for desired composition, so as to form a film.OnIt states in method, from the viewpoint of barrier properties for gases and the composition reproducibility of layer that is formed, [the inorganic A] that is used in the present inventionIt is preferable to use the sputtering methods of mixed sintering material for the forming method of layer.
[the layer of the coexisting phase containing zinc sulphide and silica：It is B layers inorganic]
It is ([inorganic for the layer of the coexisting phase containing zinc sulphide and silica for the inorganic layer for being preferably used as the present inventionB] layer) it illustrates.Make " ZnS-SiO it should be noted that being sometimes also abbreviated " zinc sulphide-silica coexisting phase "2”.SeparatelyOutside, for silica (SiO2), the difference of condition when being generated according to it, generation sometimes and the silicon of above-mentioned composition formula and oxygenComposition ratio substance (SiO~SiO slightly devious2), but silica or SiO are denoted as in this specification2, formed with thisIt is handled.About the deviation with the generation of the chemical formula of above-mentioned ratio of components, same processing mode is also used for zinc sulphide, thisRegardless of the deviation of the ratio of components caused by condition when generating in specification, zinc sulphide or ZnS are denoted as, is formed with thisIt is handled.
For by using [inorganic B] layer in the inorganic matter laminate film of the present invention so as to which barrier properties for gases be made to become excellentThe reason of good, thus it is speculated that be due to：The crystallised component and titanium dioxide contained by zinc sulphide coexist in zinc sulphide-silica coexisting phaseThe amorphous component of silicon thus tends to generation crystallite, and the crystalline growth of zinc sulphide is suppressed, and grain size becomes smaller, therefore layer is densified, oxygenThe transmission of gas and vapor is suppressed.Additionally, it is believed that inhibit zinc sulphide-silica containing zinc sulphide of crystalline growth commonPhase is deposited, compared with the layer only formed by inorganic oxide or metal oxide, flexibility is also excellent, therefore, in heat, from outsideStress under the action of be not easy to generate crackle, by using [inorganic B] layer, the gas caused by crackle generates can be inhibitedBarrier property reduces.
For the composition of [inorganic B] layer, preferably with respect to for the total of zinc sulphide and silica, mole of zinc sulphideIt is 0.7~0.9 to divide rate.If for the total of zinc sulphide and silica, the mole fraction of zinc sulphide is more than 0.9,The oxide for then inhibiting zinc sulphide crystalline growth is insufficient, and therefore, gap section, defect part increase, and cannot be advised sometimesFixed barrier properties for gases.If in addition, for the total of zinc sulphide and silica, the mole fraction of zinc sulphide is less than0.7, then the amorphous component increase of the silica inside [inorganic B] layer, the flexibility reduction of layer, sometimes in heat, from outsideStress under the action of be easy to crack.For the total of zinc sulphide and silica, the mole fraction of zinc sulphideMore preferably ranging from 0.75~0.85.
For the ingredient contained by [inorganic B] layer, if zinc sulphide and silica above-mentioned composition range and beMain component is not particularly limited, and can further contain such as silicon (Si), aluminium (Al), zinc (Zn), titanium (Ti), zirconium(Zr), other simple substance of element such as tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta), palladium (Pd) or carbide, oxygenThe compounds such as compound, nitride, sulfide, can be containing one or more in them.Herein, so-called main component, refers toMore than the 50 mass % of composition for [inorganic B] layer, preferably more than 60 mass %, more preferable more than 80 mass %.
For the composition of [inorganic B] layer, by being formed with equal the forming of mixed sintering material used during forming layer,Therefore, by using the mixed sintering material formed corresponding with purpose, the composition of [inorganic B] layer can be adjusted.
For the composition analysis of [inorganic B] layer, the ratio of components of zinc and silicon, base is obtained by ICP emission spectroanalysis firstQuantitative analysis is carried out to each element using Rutherford backscattering method in the value, so as to understand zinc sulphide, silica and containThe ratio of components of other inorganic oxides.ICP emission spectroanalysis be can by luminescent spectrum (sample is imported together with argon gas etc. fromGenerated during daughter light source portion) while the analysis method of multielement is measured, it can be used in composition analysis.In addition, rutherford carries on the backIn scattering method, to sample irradiation by the charge particle that accelerates under high voltages, according to from the charge particle wherein to reboundQuantity, energy know the ratio of components of each element into the determining, quantitative of row element.It should be noted that since [inorganic B] layer isThe composite bed of sulfide and oxide, so being carried out using the Rutherford backscattering method that the ratio of components that can carry out sulphur and oxygen is analyzedAnalysis.On inorganic layer it is laminated have resin layer when, remove and asked using X ray reflection rate method by ion(ic) etching, liquid processingAfter the caliper portion gone out, analyzed using ICP emission spectroanalysis and Rutherford backscattering method.
The method that [inorganic B] layer is formed on sheet material (i) and on the substrate layer of sheet material (ii), is not particularly limited, can be withUsing zinc sulphide and the mixed sintering material of silica, pass through the formation such as vacuum vapour deposition, sputtering method, ion plating method.It usesIt is during the monomer material of zinc sulphide and silica, zinc sulphide and silica is same by different evaporation sources or sputtering electrode respectivelyWhen be deposited or sputtering, by they mix become desired composition, so as to form film.In these methods, from gas barrierProperty and the composition reproducibility of layer that is formed from the viewpoint of, the forming method of [inorganic B] layer that uses of the present invention more preferably usesThe sputtering method of mixed sintering material.
[purposes example]
The inorganic matter laminate film of the present invention can be used in the electronic equipments such as solar cell, display body.
As solar cell, it is preferably used as silicon class solar cell, compounds solar cell, organic solar energyThe containment member of battery etc., the barrier properties for gases and adhesiveness of inorganic matter laminate film of the invention are excellent, therefore, pass through fittingOn PET resin film, fluororesin film in composition solar cell backboard, barrier of the backboard to vapor can be significantly increasedThe durability of backboard and solar cell can be significantly increased in property.
Furthermore it is possible to be preferably used as the touch panel as display body, Electronic Paper, liquid crystal display, organic el display,The containment member of organic EL illuminating etc..
It is laminated by the inorganic matter that the present invention is bonded in the laminated transparent conductive film for having ITO etc. during for touch panelSheet material can improve the barrier properties for gases of transparent conductive film, and thus, it is possible to prevent the bad of the transparent conductive film as caused by vaporChange.
As Electronic Paper, liquid crystal display, organic el display, organic EL illuminating when containment member when, for example, makeDurings with the flexible electronic paper of film, liquid crystal display, organic el display, organic EL illuminating etc., by forming the saturating of the productThe inorganic matter laminate film of the upper fitting present invention such as bright conductive film, diffusion barrier, polarizer will have using adhesive, binding agentIts whole face is sealed by the arbitrary part sealing of machine EL element, can show high gas-obstructing character, and can be inReveal flexibility, therefore, it is possible to realize the durability of flexible electronic paper, liquid crystal display, organic el display, organic EL illuminating etc.It improves, long lifetime.
[embodiment]
(embodiment A1)
(formation of sheet material (i))
As sheet material formation ingredient, to form the side for methyl methacrylate/polystyrene=90/10 [mass ratio]Formula is mixed, and then, is added 0.5 mass % azodiisobutyronitriles relative to methyl methacrylate and is caused as thermal polymerizationAgent obtains the composition of sheet material formation.It should be noted that so-called herein add 0.5 relative to methyl methacrylateQuality % refers to add 0.5 matter when sheet material formation is set as 100 mass % with the amount of the methyl methacrylate contained by ingredientMeasure %.In this example, specifically, for methyl methacrylate/polystyrene/azodiisobutyronitrile=90/10/0.5* [matterMeasure ratio] (* 0.5 is calculated by 0.5 × 90 ÷ 100).It is above-mentioned be expressed in it is identical in the following contents.
Next, in 80 DEG C of heating the composition of the above sheet formation is made its polymerization for 60 minutes, 50 μm of thickness is formedSheet material.The sheet material is the sheet material (sheet material (i)) of single layer structure.The sheet material (i) is by ingredient without crosslinking component, in addition itsNon-conforming state and formed, formed structural cycle be 96 μm island structure phase separation structure.
(formation of inorganic layer)
Prepare the agglomerated material i.e. sputtering target formed by silica, it is (following to be placed in sputtering chemical vapor deposition unitReferred to as sputtering CVD device) in.
The vacuum degree of above-mentioned sputtering CVD device is made to be 2 × 10 next, importing argon gas-1Pa is applied by high frequency electric sourceInput electric power 500W, thus generates argon plasma, by sputtering at layer of the formation containing silicon compound in the above sheet (i)As inorganic layer, it is 100nm to make layer thickness.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is single layer structureSheet material (sheet material (i)), be in addition morphogenetic by the non-conforming shape of ingredient without crosslinking component, form structural cycle as 96 μThe phase separation structure of the island structure of m.In addition, inorganic layer is the layer containing silicon compound, the inorganic matter of the present embodiment is laminatedSheet material shows height compared with following Comparative examples As 1 (sheet material uses (compatible state) sheet material without phase separation structure)Barrier properties for gases.
(embodiment A2)
(formation of sheet material (i))
As sheet material formation ingredient, to form the side for methyl methacrylate/polystyrene=85/15 [mass ratio]Formula is mixed, and then adds 0.5 mass % azodiisobutyronitriles as thermal polymerization relative to methyl methacrylate,Obtain the composition of sheet material formation.
Next, in 80 DEG C of heating the composition of the above sheet formation is made its polymerization for 60 minutes, 50 μm of thickness is formedSheet material.The sheet material is the sheet material (sheet material (i)) of single layer structure.The sheet material (i) is in addition by the non-of ingredient without crosslinking componentWhat compatible state was formed, form the phase separation structure for the island structure that structural cycle is 54 μm.
(formation of inorganic layer)
Identically with embodiment A1, the layer for containing silicon compound is formed in the above sheet (i) as inorganic layer, makes layerThickness be 100nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is single layer structureSheet material (sheet material (i)), be in addition morphogenetic by the non-conforming shape of ingredient without crosslinking component, foring structural cycle isThe phase separation structure of 54 μm of island structure.In addition, inorganic layer is the layer containing silicon compound, the inorganic layer of the present embodimentSheet material is closed, compared with following Comparative examples As 1 (sheet material uses (compatible state) sheet material without phase separation structure), displayGo out high gas-obstructing character.
(embodiment A3)
(formation of sheet material (i))
As sheet material formation ingredient, to form the side for methyl methacrylate/polystyrene=80/20 [mass ratio]Formula is mixed, and then adds 0.5 mass % azodiisobutyronitriles as thermal polymerization relative to methyl methacrylate,Obtain the composition of sheet material formation.
Next, in 80 DEG C of heating the composition of the above sheet formation is made its polymerization for 60 minutes, 50 μm of thickness is formedSheet material.The sheet material is the sheet material (sheet material (i)) of single layer structure.The sheet material (i) is in addition by the non-of ingredient without crosslinking componentWhat compatible state was formed, form the phase separation structure for the island structure that structural cycle is 45 μm.
(formation of inorganic layer)
Identically with embodiment A1, the layer for containing silicon compound is formed in the above sheet (i) as inorganic layer, makes layerThickness be 100nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is single layer structureSheet material (sheet material (i)), be in addition morphogenetic by the non-conforming shape of ingredient without crosslinking component, foring structural cycle isThe phase separation structure of 45 μm of island structure.In addition, inorganic layer is the layer containing silicon compound, the inorganic layer of the present embodimentIt is preferred scope that sheet material, which is closed, by making the structural cycle of the phase separation structure of sheet material, compared with embodiment A1, A2, shows high gasBody barrier property.
(embodiment A4)
(formation of sheet material (i))
As sheet material formation ingredient, to form the side for methyl methacrylate/polystyrene=70/30 [mass ratio]Formula is mixed, and then adds 0.5 mass % azodiisobutyronitriles as thermal polymerization relative to methyl methacrylate,Obtain the composition of sheet material formation.
Next, in 80 DEG C of heating the composition of the above sheet formation is made its polymerization for 60 minutes, 50 μm of thickness is formedSheet material.The sheet material is the sheet material (sheet material (i)) of single layer structure.The sheet material (i) is in addition by the non-of ingredient without crosslinking componentWhat compatible state was formed, form the phase separation structure for the island structure that structural cycle is 1.3 μm.
(formation of inorganic layer)
Identically with embodiment A1, the layer for containing silicon compound is formed in the above sheet (i) as inorganic layer, makes layerThickness be 100nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is single layer structureSheet material (sheet material (i)), be in addition morphogenetic by the non-conforming shape of ingredient without crosslinking component, foring structural cycle isThe phase separation structure of 1.3 μm of island structure.In addition, inorganic layer is the layer containing silicon compound, the inorganic matter of the present embodimentLaminate film is more preferable range by making the structural cycle of the phase separation structure of sheet material, compared with embodiment A1, A2, is shownHigh gas-obstructing character.
(embodiment A5)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl acrylate/polymethyl methacrylate (PMMA)The mode of=10/90 [mass ratio] is mixed, and then as Photoepolymerizationinitiater initiater, addition is as 2- methyl-1s-[4- (first sulphurBase) phenyl] -2- morpholinyl -1- acetone IRGACURE 907 (BASF AG's system) and as 2- benzyl -2- dimethylaminos -The IRGACURE 369 (BASF AG's system) of 1- (4- morpholino phenyls) -1- butanone is respectively relative to methyl acrylate addition 2.5Quality % (amounts to 5 mass %), then, adds in the mixed solvent of ethyl acetate/cyclohexanone=70/30 [mass ratio] thereto,It is diluted until solid component concentration is 10 mass %, is modulated into the coating fluid of substrate layer formation.
Next, using micro gravure coating method (intaglio plate wire size (gravure line number) 80R, intaglio plate speed ratio(gravure rotation ratio) 100%) by the coating solution of above-mentioned substrate layer formation in poly terephthalic acid secondOn diol ester film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, forms the lining of 1 μm of thicknessBottom.The sheet material is the sheet material (sheet material (ii)) of laminate structures.The substrate layer of the sheet material (ii) be free of crosslinking component, but byElectromagnetic wave, that is, ultraviolet light is irradiated when the ingredient of substrate layer is compatible state, forms phase separation structure, foring structural cycle isThe phase separation structure of 0.7 μm of island structure.
(formation of inorganic layer)
Identically with embodiment A1, on the substrate layer of the above sheet (ii), the layer for containing silicon compound is formed as nothingMachine nitride layer, the thickness for making layer are 100nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), substrate layer be free of crosslinking component, but byThe ingredient of substrate layer be compatible state when irradiate electromagnetic wave, that is, ultraviolet light, formed phase separation structure, form with embodiment A1~The phase separation structure of the island structure in A4 structure compared periods smaller (for 0.7 μm).In addition, inorganic layer is containing silicon compoundLayer, the inorganic matter laminate film of the present embodiment by make substrate layer phase separation structure structural cycle be than embodiment A1~The preferred ranges of A4, compared with embodiment A1~A4, show high gas-obstructing character.
(embodiment A6)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment A5, the sheet material (sheet material (ii)) of the laminate structures with substrate layer, the substrate layer are obtainedCrosslinking component is not contained, but phase separation structure is formed by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible state, thusForm the phase separation structure for the island structure that structural cycle is 0.7 μm.
(formation of inorganic layer)
Prepare formed by zinc oxide, silica and aluminium oxide mixed sintering material i.e. sputtering target (form mass ratio=Zinc oxide/silica/alumina=77.0/20.0/3.0), it is arranged in sputtering CVD device.
Next, argon gas and oxygen are imported when oxygen partial pressure is 10% so that the vacuum of above-mentioned sputtering CVD deviceSpend is 2 × 10-1Pa applies input electric power 500W by using DC power supply, argon gas oxygen gas plasma is generated, in sheet above[inorganic A] layer is formed by sputtering on the substrate layer of material (ii) and is used as inorganic layer, the thickness for making layer is 150nm.The inorganic matterThe composition of layer is as follows：ZnO is 71.2 mass %, Al2O3For 3.7 mass %, SiO2For 25.1 mass %, ZnO and Al2O3Always containIt measures as 74.9 mass %.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.In addition, inorganic layer is [inorganic A] layer, the inorganic matter of the present embodimentLaminate film is by making inorganic layer for preferred embodiment, and (substrate layer, which uses, does not have phase with embodiment A5 and following Comparative examples As 2The substrate layer of separated structure (compatible state)) it compares, show higher barrier properties for gases.
(embodiment A7)
(formation of the substrate layer of sheet material (ii))
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
Next, as substrate layer formation ingredient, to form as methyl acrylate/polymethyl methacrylate (PMMA)The mode of=20/80 [mass ratio] is mixed, and then as Photoepolymerizationinitiater initiater, addition is as 2- methyl-1s-[4- (first sulphurBase) phenyl] -2- morpholinyl -1- acetone IRGACURE 907 (BASF AG's system) and as 2- benzyl -2- dimethylaminos -The IRGACURE 369 (BASF AG's system) of 1- (4- morpholino phenyls) -1- butanone is respectively relative to methyl acrylate addition 2.5Quality % (amounts to 5 mass %), then, adds in the mixed solvent of ethyl acetate/cyclohexanone=70/30 [mass ratio] thereto,It is diluted until solid component concentration is 10 mass %, is modulated into the coating fluid of substrate layer formation.
Next, using micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution in polyethylene terephthalate film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2According toPenetrating ultraviolet light makes its polymerization, forms the substrate layer of 1 μm of thickness.The sheet material is the sheet material (sheet material (ii)) of laminate structures, substrate layerWithout crosslinking component, but by the ingredient in substrate layer be compatible state when irradiate electromagnetic wave, that is, ultraviolet light, formed phase separation knotStructure forms the phase separation structure for the co-continuous structure that structural cycle is 0.15 μm in substrate layer.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), substrate layer be free of crosslinking component, but byElectromagnetic wave, that is, ultraviolet light is irradiated when the substrate layer constituent different from embodiment A6 is compatible state, forms phase separation knotStructure forms the phase point of (for 0.15 μm) smaller from the embodiment A6 structure compared periods and the different co-continuous structure of planformFrom structure.In addition, inorganic layer is [inorganic A] layer, in the inorganic matter laminate film of the present embodiment, by the way that substrate layer is made to be formed altogetherThe phase separation structure (for the planform different from embodiment A6) of continuous structure, compared with embodiment A6, can adjust gasBarrier property.
(embodiment A8)
(formation of the substrate layer of sheet material (ii))
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
Next, as substrate layer formation ingredient, to form as dipentaerythritol hexaacrylate/polymethylacrylic acidThe mode of methyl esters (PMMA)=20/80 [mass ratio] is mixed, then as Photoepolymerizationinitiater initiater, addition as 2- methyl-The IRGACURE 907 (BASF AG's system) of 1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone and conduct 2- benzyls -2- twoThe IRGACURE 369 (BASF AG's system) of methylamino -1- (4- morpholino phenyls) -1- butanone, was respectively relative to for two seasons penta 4Six acrylate of alcohol adds 2.5 mass % (amounting to 5 mass %), then, adds in ethyl acetate/cyclohexanone=70/30 theretoThe mixed solvent of [mass ratio], be diluted until solid component concentration be 10 mass %, be modulated into the painting of substrate layer formationCloth liquid.
Next, using micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution in polyethylene terephthalate film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2According toPenetrating ultraviolet light makes its polymerization, forms the substrate layer of 1 μm of thickness.The sheet material is the sheet material (sheet material (ii)) of laminate structures, substrate layerContaining crosslinking component, and phase separation structure is formd by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, served as a contrastThe phase separation structure for the co-continuous structure that structural cycle is 0.093 μm is formd in bottom.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face laminate substrates layer laminate structures sheet material (sheet material (ii)), substrate layer is different from embodiment A7, is containing friendshipWhen the constituent for the substrate layer being unified into point is compatible state phase separation structure, substrate are formed by irradiating electromagnetic wave i.e. ultraviolet lightThe phase separation structure of the co-continuous structure of (for 0.093 μm) smaller with the embodiment A7 structure compared periods is formd in layer.In addition,Inorganic layer is [inorganic A] layer, and the inorganic matter laminate film of the present embodiment is by making the structure of the phase separation structure of substrate layer allPhase is range more preferred than embodiment A7, compared with embodiment A7, shows high barrier properties for gases.
(embodiment A9)
(formation of the substrate layer of sheet material (ii))
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
Next, as substrate layer formation ingredient, to form as dipentaerythritol hexaacrylate/polymethylacrylic acidThe mode of methyl esters (PMMA)=80/20 [mass ratio] is mixed, then as Photoepolymerizationinitiater initiater, addition as 2- methyl-The IRGACURE 907 (BASF AG's system) of 1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone and conduct 2- benzyls -2- twoThe IRGACURE 369 (BASF AG's system) of methylamino -1- (4- morpholino phenyls) -1- butanone, was respectively relative to for two seasons penta 4Six acrylate of alcohol adds 2.5 mass % (amounting to 5 mass %), then adds in ethyl acetate/cyclohexanone=70/30 theretoThe mixed solvent of [mass ratio], be diluted until solid component concentration be 10 mass %, be modulated into the painting of substrate layer formationCloth liquid.
Next, using micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution in polyethylene terephthalate film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2According toPenetrating ultraviolet light makes its polymerization, forms the substrate layer of 1 μm of thickness.The sheet material is the sheet material (sheet material (ii)) of laminate structures, substrate layerContaining crosslinking component, and phase separation structure, substrate are formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible stateThe phase separation structure for the co-continuous structure that structural cycle is 0.082 μm is formd in layer.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), substrate layer contains crosslinking component, and withThe component ratio of the composition of substrate layers different embodiment A8 forms phase under compatible state by irradiating electromagnetic wave i.e. ultraviolet lightSeparated structure, the phase that the co-continuous structure of (for 0.082 μm) smaller with the embodiment A7 structure compared periods is formed in substrate layer are dividedFrom structure.In addition, inorganic layer is [inorganic A] layer, and in the inorganic matter laminate film of the present embodiment, the ingredient of substrate layer and implementationExample A8 is identical, but the ratio by changing composition, can adjust barrier properties for gases.
(embodiment A10)
(formation of the substrate layer of sheet material (ii))
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
Next, as substrate layer formation ingredient, to form as pentaerythritol tetraacrylate/poly-methyl methacrylateThe mode of ester (PMMA)=80/20 [mass ratio] is mixed, then as Photoepolymerizationinitiater initiater, addition as 2- methyl-1s-The IRGACURE 907 (BASF AG's system) of [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone and conduct 2- benzyl -2- diformazansThe IRGACURE 369 (BASF AG's system) of base amino -1- (4- morpholino phenyls) -1- butanone, is respectively relative to pentaerythrite fourAcrylate adds 2.5 mass % (amounting to 5 mass %), then adds in ethyl acetate/cyclohexanone=70/30 [quality theretoThan] mixed solvent, be diluted until solid component concentration is 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, using micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution in polyethylene terephthalate film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2According toPenetrating ultraviolet light makes its polymerization, forms the substrate layer of 1 μm of thickness.The sheet material is the sheet material (sheet material (ii)) of laminate structures, substrate layerContaining crosslinking component, and phase separation structure, substrate are formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible stateThe phase separation structure for the co-continuous structure that structural cycle is 0.051 μm is formed in layer.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), substrate layer contains crosslinking component, and withWhen the constituent of substrate layers different embodiment A9 is compatible state phase separation knot is formed by irradiating electromagnetic wave i.e. ultraviolet lightStructure forms the phase separation structure with the co-continuous structure in embodiment A9 structure compared periods smaller (for 0.051 μm) in substrate layer.In addition, inorganic layer is [inorganic A] layer, in the inorganic matter laminate film of the present embodiment, the component ratio of the composition of substrate layer withEmbodiment A9 is identical, but the structural cycle of phases were separated by changing ingredient structure changes, so as to adjust barrier properties for gases.
(embodiment A11)
(formation of the substrate layer of sheet material (ii))
In addition to 1.9J/cm2Irradiation ultraviolet light makes other than substrate layers of polymer, identically with embodiment A10, obtains having liningThe sheet material of the laminate structures of bottom, which contains crosslinking component, and changes electromagnetic wave when ingredient is compatible stateThe accumulated light of ultraviolet light is irradiated to form phase separation structure, and the co-continuous structure that structural cycle is 0.024 μm is consequently formedPhase separation structure.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), for substrate layer, comprising being cross-linked intoPass through when the constituent of the substrate layer divided is compatible state and electricity is irradiated under conditions of the accumulated light height compared with embodiment A10Magnetic wave, that is, ultraviolet light and form phase separation structure, in substrate layer formed with the embodiment A10 structure compared periods it is smaller (for0.024 μm) co-continuous structure phase separation structure.In addition, inorganic layer is [inorganic A] layer, the inorganic layer of the present embodimentIt closes in sheet material, by the way that the structural cycle of phase separation structure of substrate layer is made to be range more preferred than embodiment A10, with embodimentA10 is compared, and shows high barrier properties for gases.
(embodiment A12)
(formation of the substrate layer of sheet material (ii))
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
Next, as substrate layer formation ingredient, formed with being formed as pentaerythritol tetraacrylate/polymethylThe mode of sour methyl esters (PMMA)=90/10 [mass ratio] is mixed, and then as Photoepolymerizationinitiater initiater, addition is as 2- firstIRGACURE 907 (BASF AG's system) and conduct the 2- benzyl of base -1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone -The IRGACURE 369 (BASF AG's system) of 2- dimethylaminos -1- (4- morpholino phenyls) -1- butanone, relative to pentaerythriteTetraacrylate adds 2.5 mass % (amounting to 5 mass %) respectively, then adds in ethyl acetate/cyclohexanone=70/30 theretoThe mixed solvent of [mass ratio], be diluted until solid component concentration be 10 mass %, be modulated into the painting of substrate layer formationCloth liquid.
Next, using micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution in polyethylene terephthalate film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2According toPenetrating ultraviolet light makes its polymerization, forms the substrate layer of 1 μm of thickness.The sheet material is the sheet material (sheet material (ii)) of laminate structures, substrate layerContaining crosslinking component, and phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, served as a contrastThe phase separation structure for the co-continuous structure that structural cycle is 0.012 μm is formed in bottom.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), substrate layer contains crosslinking component, and withThe component ratio of the composition of substrate layers different embodiment A10 is formed under compatible state by irradiating electromagnetic wave i.e. ultraviolet lightPhase separation structure forms the co-continuous knot of (for 0.012 μm) smaller with embodiment A10, the A11 structure compared period in substrate layerThe phase separation structure of structure.In addition, inorganic layer is [inorganic A] layer, in the inorganic matter laminate film of the present embodiment, served as a contrast by changingThe component ratio of the composition of bottom (does not change the purple irradiated when ingredient is compatible state as shown in embodiment A11The irradiation condition of outside line), the structural cycle of the phase separation structure of substrate layer can be adjusted to preferred scope, with embodiment A10Compared to showing high barrier properties for gases.
(embodiment A13)
(formation of the substrate layer of sheet material (ii))
In addition to 1.9J/cm2Irradiation ultraviolet light makes other than substrate layers of polymer, identically with embodiment A12, obtains having liningThe sheet material (sheet material (ii)) of the laminate structures of bottom, the substrate layer contain crosslinking component, and when ingredient is compatible stateThe accumulated light for changing electromagnetic wave, that is, ultraviolet light is irradiated to form phase separation structure, and it is 0.006 μm that structural cycle, which is consequently formed,Co-continuous structure phase separation structure.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), for substrate layer, by containing being cross-linked intoThe constituent of the substrate layer divided irradiates electromagnetic wave when being compatible state under conditions of the accumulated light height compared with embodiment A12That is ultraviolet light, and phase separation structure is formd, it (is 0.006 to be formd in substrate layer smaller with the embodiment A12 structure compared periodsμm) co-continuous structure phase separation structure.In addition, inorganic layer is [inorganic A] layer, the inorganic matter laminate film of the present embodimentThe structural cycle of the phase separation structure of substrate layer is small compared with embodiment A12, can adjust barrier properties for gases.
(embodiment A14)
(formation of the substrate layer of sheet material (ii))
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
Next, as substrate layer formation ingredient, to form as trimethylolpropane trimethacrylate/polymethylThe mode of sour methyl esters (PMMA)=80/20 [mass ratio] is mixed, and then as Photoepolymerizationinitiater initiater, addition is as 2- firstIRGACURE 907 (BASF AG's system) and conduct the 2- benzyl of base -1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone -The IRGACURE 369 (BASF AG's system) of 2- dimethylaminos -1- (4- morpholino phenyls) -1- butanone, is respectively relative to three hydroxylsPropane tri adds 2.5 mass % (amount to 5 mass %), then add in thereto ethyl acetate/cyclohexanone=The mixed solvent of 70/30 [mass ratio], be diluted until solid component concentration be 10 mass %, be modulated into substrate layer formed useCoating fluid.
Next, using micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution in polyethylene terephthalate film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2According toPenetrating ultraviolet light makes its polymerization, forms the substrate layer of 1 μm of thickness.The sheet material is the sheet material (sheet material (ii)) of laminate structures, substrate layerContaining crosslinking component, and when ingredient is compatible state by irradiating electromagnetic wave i.e. ultraviolet light so as to form phase separation structure,The phase separation structure for the co-continuous structure that structural cycle is 0.003 μm is formed in substrate layer.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.Sheet material in the inorganic matter laminate film of the present embodiment is in substrate layerSide face be laminated with substrate layer laminate structures sheet material (sheet material (ii)), for substrate layer, by containing being cross-linked intoIrradiation electromagnetic wave, that is, ultraviolet light is so as to form phase separation structure, substrate layer when the constituent of the substrate layer divided is compatible stateMiddle formation and the phase separation structure of the co-continuous structure of embodiment A13 structure compared periods smaller (for 0.003 μm).In addition, nothingMachine nitride layer is [inorganic A] layer, the inorganic matter laminate film of the present embodiment phase separation structure of substrate layer compared with embodiment A12Structural cycle is small, can adjust barrier properties for gases.
(embodiment A15)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment A10, the sheet material (sheet material (ii)) of the laminate structures with substrate layer, the substrate layer are obtainedContaining crosslinking component, and by irradiation electromagnetic wave, that is, ultraviolet light formation phase separation structure when ingredient is compatible state, thusForm the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Other than making thickness for 120nm, identically with embodiment A6, formed on the substrate layer of the above sheet (ii)[inorganic A] layer is as inorganic layer.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.In addition, inorganic layer is [inorganic A] layer, the inorganic matter of the present embodimentLaminate film can adjust barrier properties for gases by changing the thickness of inorganic layer compared with embodiment A10.
(embodiment A16)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment A10, the sheet material (sheet material (ii)) of the laminate structures with substrate layer, the substrate layer are obtainedContaining crosslinking component, and by irradiation electromagnetic wave, that is, ultraviolet light formation phase separation structure when ingredient is compatible state, thusForm the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Other than making thickness for 100nm, identically with embodiment A6, formed on the substrate layer of the above sheet (ii)[inorganic A] layer is as inorganic layer.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.In addition, inorganic layer is [inorganic A] layer, the inorganic matter of the present embodimentLaminate film by changing the thickness of inorganic layer, can adjust barrier properties for gases compared with embodiment A10, A15.
(embodiment A17)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment A10, the sheet material (sheet material (ii)) of the laminate structures with substrate layer, the substrate layer are obtainedPhase separation structure is formed containing crosslinking component, and by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible state, fromAnd form the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Other than making thickness for 50nm, identically with embodiment A6, [nothing is formed on the substrate layer of the above sheet (ii)Machine A] layer is as inorganic layer.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.In addition, inorganic layer is [inorganic A] layer, the inorganic matter of the present embodimentLaminate film can adjust barrier properties for gases by changing the thickness of inorganic layer compared with embodiment A10, A15, A18.
(embodiment A18)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment A10, the sheet material (sheet material (ii)) of the laminate structures with substrate layer, the substrate layer are obtainedPhase separation structure is formed containing crosslinking component, and by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible state, fromAnd form the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Other than making thickness for 15nm, identically with embodiment A6, [nothing is formed on the substrate layer of the above sheet (ii)Machine A] layer is as inorganic layer.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.In addition, inorganic layer is [inorganic A] layer, the inorganic matter of the present embodimentLaminate film is thinning by making the thickness of inorganic layer, and compared with embodiment A10, A15, A16, A17, barrier properties for gases is deteriorated.
(embodiment A19)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment A10, the sheet material of laminate structures with substrate layer is obtained, the substrate layer, which contains, to be cross-linked intoPoint, and by irradiation electromagnetic wave, that is, ultraviolet light formation phase separation structure when ingredient is compatible state, so as to form structure weekPhase is the phase separation structure of 0.051 μm of co-continuous structure.
(formation of inorganic layer)
Prepare the agglomerated material i.e. sputtering target (molar composition ratio=zinc sulphide/dioxy formed by zinc sulphide and silicaSiClx=80/20), it is arranged in sputtering CVD device.
The vacuum degree of above-mentioned sputtering CVD device is made to be 2 × 10 next, importing argon gas-1Pa is applied using high frequency electric sourceInput electric power 500W, thus generates argon plasma, and [inorganic B] is formed on the substrate layer by sputtering at the above sheet (ii)For layer as inorganic layer, the thickness for making layer is 150nm.The composition of the inorganic layer is as follows：ZnS is 86.7 mass %, SiO2For13.3 quality %.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.In addition, inorganic layer is [inorganic B] layer, the inorganic matter of the present embodimentLaminate film in substrate layer by having phase separation structure, with following Comparative examples As 3 (using (compatible without phase separation structureState) substrate layer) compared to higher barrier properties for gases is shown, even if in addition forming the inorganic matter different from embodiment A10Layer also presents the improvement effect of barrier properties for gases.
(embodiment A20)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment A10, the sheet material (sheet material (ii)) of the laminate structures with substrate layer, the substrate layer are obtainedContaining crosslinking component, and by irradiation electromagnetic wave, that is, ultraviolet light formation phase separation structure when ingredient is compatible state, thusForm the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Prepare the evaporation material containing aluminium, be placed in vacuum deposition apparatus.
Next, using above-mentioned vacuum deposition apparatus, by leading while using resistance heating manner by aluminium steamEnter the vacuum vapour deposition of oxygen, formed on the substrate layer of the above sheet (ii) and contain the layer of aluminium compound as inorganic layer,The thickness for making layer is 20nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.In addition, inorganic layer is the layer containing aluminium compound, the present embodimentInorganic matter laminate film (does not have by having phase separation structure in substrate layer with following Comparative examples As 4 using in substrate layerHave (compatible state) substrate layer of phase separation structure) it compares, show higher barrier properties for gases.
(embodiment A21)
(formation of the substrate layer of sheet material (ii))
Prepare the poly (ethylene naphthalate) film of 50 μm of thickness.
Next, identically with embodiment A10, obtain the sheet material (sheet material (ii)) of the laminate structures with substrate layer, instituteIt states substrate layer and contains crosslinking component, and pass through irradiation electromagnetic wave, that is, ultraviolet light formation phase separation knot when ingredient is compatible stateStructure, so as to form the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.The inorganic matter laminate film of the present embodiment uses poly- naphthalenedicarboxylic acid second twoAlcohol ester film, on it laminated substrate layer and inorganic layer identically with embodiment A10.Even if by polyethylene terephthalateMembrane change is poly (ethylene naphthalate) film, also shows that high gas-obstructing character.
(embodiment A22)
(formation of the substrate layer of sheet material (ii))
Prepare cycloolefin copolymer resin film (Gunze (strain) systems, the trade name of 100 μm of thickness：" F films " F1).
Next, identically with embodiment A10, obtain the sheet material (sheet material (ii)) of the laminate structures with substrate layer, instituteIt states substrate layer and contains crosslinking component, and pass through irradiation electromagnetic wave, that is, ultraviolet light formation phase separation knot when ingredient is compatible stateStructure, so as to form the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.The inorganic matter laminate film of the present embodiment uses cycloolefin copolymer resinFilm, on it laminated substrate layer and inorganic layer identically with embodiment A10.Even if polyethylene terephthalate film is changedBecome cycloolefin copolymer resin film, also show that high gas-obstructing character.
(embodiment A23)
(formation of the substrate layer of sheet material (ii))
Prepare cycloolefin resin film (Japanese Zeon (strain) system, the trade name of 100 μm of thickness：" Zeonor films " (registrarMark) ZF-16).
Next, identically with embodiment A10, obtain the sheet material (sheet material (ii)) of the laminate structures with substrate layer, instituteIt states substrate layer and contains crosslinking component, and pass through irradiation electromagnetic wave, that is, ultraviolet light formation phase separation knot when ingredient is compatible stateStructure, so as to form the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.The inorganic matter laminate film of the present embodiment uses cycloolefin resin film,Laminated substrate layer and inorganic layer identically with embodiment A10 on it.Even if polyethylene terephthalate film is changedFor cycloolefin resin film, high gas-obstructing character is also showed that.
(Comparative examples A 1)
(formation of the substrate layer of sheet material)
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
Next, as substrate layer formation ingredient, only prepare pentaerythritol tetraacrylate, then draw as photopolymerizationAgent is sent out, adds 907 (BASF AG of IRGACURE as 2- methyl-1s-[4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetoneSystem) and 369 (BASF AG of IRGACURE as 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) -1- butanoneSystem), it is respectively relative to pentaerythritol tetraacrylate and adds 2.5 mass % (amounting to 5 mass %), then add in acetic acid theretoThe mixed solvent of ethyl ester/cyclohexanone=70/30 [mass ratio], be diluted until solid component concentration be 10 mass %, modulationInto the coating fluid of substrate layer formation.
Next, using micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution in polyethylene terephthalate film, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2According toPenetrating ultraviolet light makes its polymerization, forms the substrate layer of 1 μm of thickness.The sheet material is that laminated on the face of the side of substrate layer have substrate layerLaminate structures sheet material, but do not form phase separation structure.
(formation of inorganic layer)
Identically with embodiment A1, the layer for containing silicon compound is formed on the substrate layer of the above sheet as inorganic matterLayer, the thickness for making layer are 100nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.The inorganic matter laminate film of this comparative example is tied without phase separationIt is laminated on the sheet material of the laminate structures of structure to be formed containing the inorganic layer of silicon compound, with embodiment A1~A5 (withInorganic layer is identically formed on the substrate layer of phase separation structure) it compares, barrier properties for gases is poor.
(Comparative examples A 2)
(formation of the substrate layer of sheet material)
Identically with Comparative examples A 1, the sheet material of laminate structures with substrate layer is obtained, the substrate layer is without phase pointFrom structure.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet, makes layerThickness is 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.The inorganic matter laminate film of this Comparative examples A is tied without phase separationIt is laminated on the sheet material of the laminate structures of structure to have the inorganic layer formed by [inorganic A], with embodiment A6~A17, A21, A22, A23(inorganic layer is identically formed on the substrate layer with phase separation structure) is compared, and barrier properties for gases is poor.
(Comparative examples A 3)
(formation of the substrate layer of sheet material)
Identically with Comparative examples A 1, the sheet material of laminate structures with substrate layer is obtained, the substrate layer is without phase pointFrom structure.
(formation of inorganic layer)
Identically with embodiment A19, [inorganic B] layer is formed on the substrate layer of the above sheet, as inorganic layer, makes layerThickness be 150nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.The inorganic matter laminate film of this comparative example is without phase separation structureLaminate structures sheet material on it is laminated have the inorganic layer formed by [inorganic B], with embodiment A19 (with phase separation structureSubstrate layer on be identically formed with inorganic layer) it is poor compared to barrier properties for gases.
(Comparative examples A 4)
(formation of the substrate layer of sheet material)
Identically with Comparative examples A 1, the sheet material of laminate structures with substrate layer is obtained, the substrate layer is without phase pointFrom structure.
(formation of inorganic layer)
Identically with embodiment A20, the layer for containing aluminium compound is formed on the substrate layer of the above sheet as inorganic matterLayer, the thickness for making layer are 20nm.
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.The inorganic matter laminate film of this comparative example is without phase separation structureLaminate structures sheet material on it is laminated have the inorganic layer containing aluminium compound, with embodiment A20 (with phase separation structureInorganic layer is identically formed on substrate layer) it is poor compared to barrier properties for gases.
(Comparative examples A 5)
(formation of the substrate layer of sheet material)
Prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (noteVolume trade mark) U48)).
As sheet material formation ingredient, to form the side for methyl methacrylate/polystyrene=50/50 [mass ratio]Formula is mixed, and then adds 0.5 mass % azodiisobutyronitriles as thermal polymerization relative to methyl methacrylate,Obtain the coating fluid of sheet material formation.
Next, in 80 DEG C of heating the coating fluid of the above sheet formation is made its polymerization for 60 minutes, 50 μm of thickness is formedSheet material.The sheet material is single layer structure, is in addition morphogenetic by the non-conforming shape of ingredient, formation finishes without crosslinking componentThe structure period is the phase separation structure of 104 μm of island structure.It should be noted that the structural cycle is measured even if using B methodsMore than 100 μm.
(formation of inorganic layer)
Identically with embodiment A6, [inorganic A] layer is formed as inorganic layer in the above sheet, the thickness for making layer is150nm。
(inorganic matter laminate film)
Obtain inorganic matter laminate film as described above.For the inorganic matter laminate film of this comparative example, although sheet material hasThe phase separation structure of island structure, but structural cycle is 104 μm, it is bigger than desired range, therefore, compared with embodiment A6,Although being identically formed inorganic layer, barrier properties for gases is poor.
(embodiment B1)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl methacrylate/polystyrene=90/10 [matterAmount ratio] mode mixed, then relative to methyl methacrylate add 0.5 mass % azodiisobutyronitriles as hot polymerizationClose initiator, then thereto add in toluene/acetone=50/50 [quality %] mixed solvent, be diluted until solid-state intoDivide a concentration of 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, make within 60 minutes its polymerization in 80 DEG C of heating, form the substrate layer of 1 μm of thickness, layer is madeClose the sheet material (sheet material (ii)) of structure.The substrate layer of the sheet material (ii) is free of crosslinking component, is in addition the non-conforming shape by ingredientIt is morphogenetic, it is formed with the phase separation structure for the island structure that structural cycle is 96 μm.
(formation of inorganic layer)
Prepare the agglomerated material i.e. sputtering target that is formed by silica, be arranged on sputter chemical vapor deposition unit (withLower referred to as sputtering CVD device) in.
The vacuum degree of above-mentioned sputtering CVD device is made to be 2 × 10 next, importing argon gas-1Pa is applied using high frequency electric sourceInput electric power 500W, thus generates argon plasma, is formed on the substrate layer by sputtering at the above sheet (ii) and contains siliconFor the layer of compound as inorganic layer, the thickness for making layer is 100nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicIn addition substrate layer in object laminate film is morphogenetic by the non-conforming shape of ingredient, is formed with structure week without crosslinking componentPhase is the phase separation structure of 96 μm of island structure.In addition, inorganic layer is the layer containing silicon compound, the present embodiment it is inorganicObject laminate film, compared with following comparative example B1 ((compatible state) sheet material for not having phase separation structure using substrate layer),Show high gas-obstructing character.
(embodiment B2)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl methacrylate/polystyrene=85/15 [matterAmount ratio] mode mixed, then relative to methyl methacrylate add 0.5 mass % azodiisobutyronitriles as hot polymerizationClose initiator, then thereto add toluene/acetone=50/50 [mass ratio] mixed solvent, be diluted until solid-state intoDivide a concentration of 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, make within 60 minutes its polymerization in 80 DEG C of heating, form the substrate layer of 1 μm of thickness.The substrateIn addition layer is morphogenetic by the non-conforming shape of ingredient, forms the island structure that structural cycle is 54 μm without crosslinking componentPhase separation structure.
(formation of inorganic layer)
Identically with embodiment B1, the layer for containing silicon compound is formed on the substrate layer of the above sheet (ii) as inorganicNitride layer, the thickness for making layer are 100nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicIn addition substrate layer in object laminate film is morphogenetic by the non-conforming shape of ingredient, is formed with structure week without crosslinking componentPhase is the phase separation structure of 54 μm of island structure.In addition, inorganic layer is the layer containing silicon compound, the present embodiment it is inorganicObject laminate film shows higher barrier properties for gases compared with following comparative example B1.
(embodiment B3)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl methacrylate/polystyrene=80/20 [matterAmount ratio] mode mixed, then relative to methyl methacrylate add 0.5 mass % azodiisobutyronitriles as hot polymerizationClose initiator, then thereto add in toluene/acetone=50/50 [mass ratio] mixed solvent, be diluted until solid-state intoDivide a concentration of 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, make within 60 minutes its polymerization in 80 DEG C of heating, form the substrate layer of 1 μm of thickness, layer is madeClose the sheet material (sheet material (ii)) of structure.The substrate layer of the sheet material (ii) is free of crosslinking component, is in addition the non-conforming shape by ingredientIt is morphogenetic, form the phase separation structure for the island structure that structural cycle is 45 μm.
(formation of inorganic layer)
Identically with embodiment B1, the layer for containing silicon compound is formed on the substrate layer of the above sheet (ii) as inorganicNitride layer, the thickness for making layer are 100nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicIn addition substrate layer in object laminate film is morphogenetic by the non-conforming shape of ingredient, forms structural cycle without crosslinking componentPhase separation structure for 45 μm of island structure.In addition, inorganic layer is the layer containing silicon compound, the inorganic matter of the present embodimentLaminate film is preferred scope by making the structural cycle of the phase separation structure of substrate layer, is shown compared with embodiment B1, B2High gas-obstructing character.
(embodiment B4)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl methacrylate/polystyrene=70/30 [matterAmount ratio] mode mixed, then relative to methyl methacrylate add 0.5 mass % azodiisobutyronitriles as hot polymerizationClose initiator, then thereto add in toluene/acetone=50/50 [mass ratio] mixed solvent, be diluted until solid-state intoDivide a concentration of 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, make within 60 minutes its polymerization in 80 DEG C of heating, form the substrate layer of 1 μm of thickness, layer is madeClose the sheet material (sheet material (ii)) of structure.The substrate layer of the sheet material (ii) is free of crosslinking component, is in addition the non-conforming shape by ingredientIt is morphogenetic, form the phase separation structure for the island structure that structural cycle is 1.3 μm.
(formation of inorganic layer)
Identically with embodiment B1, the layer for containing silicon compound is formed on the substrate layer of the above sheet (ii) as inorganicNitride layer, the thickness for making layer are 100nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicIn addition substrate layer in object laminate film is morphogenetic by the non-conforming shape of ingredient, is formed with structure week without crosslinking componentPhase is the phase separation structure of 1.3 μm of island structure.In addition, inorganic layer is the layer containing silicon compound, the nothing of the present embodimentMachine object laminate film is preferred scope by making the structural cycle of the phase separation structure of substrate layer, compared with embodiment B1, B2, is shownHigh gas-obstructing character is shown.
(embodiment B5)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl acrylate/polymethyl methacrylate (PMMA)The mode of=10/90 [mass ratio] is mixed, and then as Photoepolymerizationinitiater initiater, addition is as 2- methyl-1s-[4- (first sulphurBase) phenyl] -2- morpholinyl -1- acetone IRGACURE 907 (BASF AG's system) and as 2- benzyl -2- dimethylaminos -The IRGACURE 369 (BASF AG's system) of 1- (4- morpholino phenyls) -1- butanone, is respectively relative to methyl acrylate and is added to2.5 mass % (amount to 5 mass %), and then, the mixing for adding in ethyl acetate/cyclohexanone=70/30 [mass ratio] thereto is moltenAgent is diluted until solid component concentration is 10 mass %, is modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer of the sheet material (ii) is free of and is cross-linked intoPoint, phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, it is 0.7 to be formed with structural cycleμm island structure phase separation structure.
(formation of inorganic layer)
Identically with embodiment B1, the layer for containing silicon compound is formed on the substrate layer of the above sheet (ii) as inorganicNitride layer, the thickness for making layer are 100nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicSubstrate layer in object laminate film is formed without crosslinking component when ingredient is compatible state by irradiating electromagnetic wave i.e. ultraviolet lightPhase separation structure forms the phase separation structure with the island structure in embodiment B1~B4 structure compared periods smaller (for 0.7 μm).In addition, inorganic layer is the layer containing silicon compound, the inorganic matter laminate film of the present embodiment is by making the phase separation of substrate layerThe structural cycle of structure is range more preferred than embodiment B1~B4, and higher gas is shown compared with embodiment B1~B4Barrier property.
(embodiment B6)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment B5, substrate layer is formed so as to which the sheet material (piece of laminate structures be made with 1 μm of thickness on base materialMaterial (ii)), the substrate layer does not contain crosslinking component, but passes through the irradiation electromagnetic wave, that is, ultraviolet linear when ingredient is compatible stateInto phase separation structure, so as to form the phase separation structure for the island structure that structural cycle is 0.7 μm.
(formation of inorganic layer)
Prepare formed by zinc oxide, silica and aluminium oxide mixed sintering material i.e. sputtering target (form mass ratio=Zinc oxide/silica/alumina=77.0/20.0/3.0), it is arranged in sputtering CVD device.
Next, the vacuum degree of above-mentioned sputtering CVD device is made to be 2 by 10%, importing argon gas and oxygen of oxygen partial pressure×10-1Pa applies input electric power 500W by using DC power supply, argon gas oxygen gas plasma is generated, in above-mentioned substrate layerUpper to be used as inorganic layer by sputtering formation [inorganic A] layer, the thickness for making layer is 150nm.The composition of the inorganic layer is as follows：ZnO is 71.2 mass %, Al2O3For 3.7 mass %, SiO2For 25.1 mass %, and ZnO and Al2O3Total content be 74.9 matterMeasure %.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.In addition, inorganic layerIt is [inorganic A] layer, the inorganic matter laminate film of the present embodiment is by making inorganic layer for preferred embodiment, with embodiment B5, followingComparative example B2 ((compatible state) sheet material for not had phase separation structure using substrate layer) is compared, and shows higher gas resistanceEvery property.
(embodiment B7)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl acrylate/polymethyl methacrylate (PMMA)The mode of=20/80 [mass ratio] is mixed, and then as Photoepolymerizationinitiater initiater, addition is as 2- methyl-1s-[4- (first sulphurBase) phenyl] -2- morpholinyl -1- acetone IRGACURE 907 (BASF AG's system) and as 2- benzyl -2- dimethylaminos -The IRGACURE 369 (BASF AG's system) of 1- (4- morpholino phenyls) -1- butanone, is respectively relative to methyl acrylate and is added to2.5 mass % (amount to 5 mass %), and then, the mixing for adding in ethyl acetate/cyclohexanone=70/30 [mass ratio] thereto is moltenAgent is diluted until solid component concentration is 10 mass %, is modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer of the sheet material (ii) is free of and is cross-linked intoPoint, phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, is so as to form structural cycleThe phase separation structure of 0.15 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicSubstrate layer in object laminate film is without crosslinking component, when the substrate layer constituent different from embodiment B6 is compatible stateBy irradiate electromagnetic wave i.e. ultraviolet light formed phase separation structure, so as to formed with the embodiment B6 structure compared periods it is smaller (for0.15 μm) and the different co-continuous structure of planform phase separation structure.In addition, inorganic layer is [inorganic A] layer, this realityThe inorganic matter laminate film of example is applied by the way that substrate layer is made to form the phase separation structure i.e. co-continuous structure different from embodiment B6Phase separation structure compared with embodiment B6, can adjust barrier properties for gases.
(embodiment B8)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as dipentaerythritol hexaacrylate/polymethylacrylic acidThe mode of methyl esters (PMMA)=20/80 [mass ratio] is mixed, then as Photoepolymerizationinitiater initiater, addition as 2- methyl-The IRGACURE 907 (BASF AG's system) of 1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone and conduct 2- benzyls -2- twoThe IRGACURE 369 (BASF AG's system) of methylamino -1- (4- morpholino phenyls) -1- butanone, relative to dipentaerythritol sixAcrylate is separately added into 2.5 mass % (amounting to 5 mass %), then adds in ethyl acetate/cyclohexanone=70/30 theretoThe mixed solvent of [mass ratio], be diluted until solid component concentration be 10 mass %, be modulated into the painting of substrate layer formationCloth liquid.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer of the sheet material (ii), which contains, to be cross-linked intoPoint, and phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, so as to form structure weekPhase is the phase separation structure of 0.093 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicSubstrate layer in object laminate film is different from embodiment B7, when the substrate layer constituent containing crosslinking component is compatible stateBy irradiate electromagnetic wave i.e. ultraviolet light formed phase separation structure, so as to formed with the embodiment B7 structure compared periods it is smaller (for0.093 μm) co-continuous structure phase separation structure.In addition, inorganic layer is [inorganic A] layer, the inorganic layer of the present embodimentIt is range more preferred than embodiment B7 that sheet material, which is closed, by making the structural cycle of the phase separation structure of substrate layer, with embodiment B7 phasesThan showing higher barrier properties for gases.
(embodiment B9)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as dipentaerythritol hexaacrylate/polymethylacrylic acidThe mode of methyl esters (PMMA)=80/20 [mass ratio] is mixed, then as Photoepolymerizationinitiater initiater, addition as 2- methyl-The IRGACURE 907 (BASF AG's system) of 1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone and conduct 2- benzyls -2- twoThe IRGACURE 369 (BASF AG's system) of methylamino -1- (4- morpholino phenyls) -1- butanone, was respectively relative to for two seasons penta 4Six acrylate of alcohol adds in 2.5 mass % (amounting to 5 mass %), then adds in ethyl acetate/cyclohexanone=70/30 theretoThe mixed solvent of [mass ratio], be diluted until solid component concentration be 10 mass %, be modulated into the painting of substrate layer formationCloth liquid.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer of the sheet material (ii), which contains, to be cross-linked intoPoint, and phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, so as to form structure weekPhase is the phase separation structure of 0.082 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicSubstrate layer in object laminate film contains crosslinking component, and with the substrate layer constituent ratio different from embodiment B8 in phaseUnder appearance state by irradiate electromagnetic wave i.e. ultraviolet light formed phase separation structure, so as to formed with the embodiment B7 structure compared periods compared withThe phase separation structure of the co-continuous structure of small (for 0.082 μm).In addition, inorganic layer is [inorganic A] layer, the present embodiment it is inorganicObject laminate film although the ingredient of substrate layer is identical with embodiment B8, by changing composition ratio, can adjust gas barrierProperty.
(embodiment B10)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as pentaerythritol tetraacrylate/poly-methyl methacrylateThe mode of ester (PMMA)=80/20 [mass ratio] is mixed, then as Photoepolymerizationinitiater initiater, addition as 2- methyl-1s-The IRGACURE 907 (BASF AG's system) of [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone and conduct 2- benzyl -2- diformazansThe IRGACURE 369 (BASF AG's system) of base amino -1- (4- morpholino phenyls) -1- butanone, is respectively relative to pentaerythrite fourAcrylate adds 2.5 mass % (amounting to 5 mass %), then adds in ethyl acetate/cyclohexanone=70/30 [quality theretoThan] mixed solvent, be diluted until solid component concentration is 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer of the sheet material (ii), which contains, to be cross-linked intoPoint, and phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, so as to form structure weekPhase is the phase separation structure of 0.051 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicSubstrate layer in object laminate film contains crosslinking component, and is compatible shape in the substrate layer constituent different from embodiment B9Phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light during state, it is smaller with the embodiment B9 structure compared periods so as to be formedThe phase separation structure of the co-continuous structure of (for 0.051 μm).In addition, inorganic layer is [inorganic A] layer, the inorganic matter of the present embodimentLaminate film, although the constituent ratio of substrate layer is identical with embodiment B9 by changing ingredient, structure that phases were separatedStructural cycle changes, and can adjust barrier properties for gases.
(embodiment B11)
(formation of the substrate layer of sheet material (ii))
In addition to 1.9J/cm2Irradiation ultraviolet light make other than substrate layers of polymer, in the same manner as embodiment B10 on base material shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer contains crosslinking component, and passes throughThe accumulated light for changing electromagnetic wave, that is, ultraviolet light when ingredient is compatible state is irradiated to form phase separation structure, is formedStructural cycle is the phase separation structure of 0.024 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.For the present embodimentSubstrate layer in inorganic matter laminate film, by the substrate layer constituent containing crosslinking component be compatible state when than realityIt applies irradiation electromagnetic wave i.e. ultraviolet light under conditions of the accumulated light of a B10 high and forms phase separation structure, formed and embodiment B10The phase separation structure of the co-continuous structure in structure compared period smaller (for 0.024 μm).In addition, inorganic layer is [inorganic A] layer,The inorganic matter laminate film of the present embodiment is more more preferable than embodiment B10 by making the structural cycle of the phase separation structure of substrate layerRange, compared with embodiment B10, show higher barrier properties for gases.
(embodiment B12)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as pentaerythritol tetraacrylate/poly-methyl methacrylateThe mode of ester (PMMA)=90/10 [mass ratio] is mixed, then as Photoepolymerizationinitiater initiater, addition as 2- methyl-1s-The IRGACURE 907 (BASF AG's system) of [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone and conduct 2- benzyl -2- diformazansThe IRGACURE 369 (BASF AG's system) of base amino -1- (4- morpholino phenyls) -1- butanone, is respectively relative to pentaerythrite fourAcrylate adds 2.5 mass % (amounting to 5 mass %), then adds in ethyl acetate/cyclohexanone=70/30 [quality theretoThan] mixed solvent, be diluted until solid component concentration is 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer of the sheet material (ii), which contains, to be cross-linked intoPoint, and phase separation structure is formed by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible state, form structural cyclePhase separation structure for 0.012 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicSubstrate layer in object laminate film contains crosslinking component, and is existed with the substrate layer constituent ratio different from embodiment B10Phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light under compatible state, is formed and embodiment B10, B11 structure compared weekThe phase separation of the co-continuous structure of phase smaller (for 0.012 μm).In addition, inorganic layer is [inorganic A] layer, the present embodiment it is inorganicBy changing the constituent ratio of substrate layer, (it is compatible not need to change as embodiment B11 in ingredient to object laminate filmThe ultraviolet irradiation condition irradiated during state), the structural cycle of the phase separation structure of substrate layer can be adjusted to preferred modelIt encloses, higher barrier properties for gases is shown compared with embodiment B10.
(embodiment B13)
(formation of the substrate layer of sheet material (ii))
In addition to 1.9J/cm2Irradiation ultraviolet light make other than substrate layers of polymer, in the same manner as embodiment B12 on base material shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer contains crosslinking component, and passes throughThe accumulated light for changing electromagnetic wave, that is, ultraviolet light when ingredient is compatible state is irradiated to form phase separation structure, is formedStructural cycle is the phase separation structure of 0.006 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.For the present embodimentSubstrate layer in inorganic matter laminate film, by the substrate layer constituent containing crosslinking component be compatible state when with than realityIrradiation electromagnetic wave i.e. ultraviolet light is so as to form phase separation structure, formation and embodiment under conditions of applying the accumulated light of a B12 highThe phase separation structure of the co-continuous structure in B12 structure compared periods smaller (for 0.006 μm).In addition, inorganic layer is [inorganic A]Layer, the structural cycle of inorganic matter laminate film phase separation structure of substrate layer compared with embodiment B12 of the present embodiment is small, can be withAdjust barrier properties for gases.
(embodiment B14)
(formation of the substrate layer of sheet material (ii))
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as trimethylolpropane trimethacrylate/polymethylThe mode of sour methyl esters (PMMA)=80/20 [mass ratio] is mixed, and then as Photoepolymerizationinitiater initiater, addition is as 2- firstIRGACURE 907 (BASF AG's system) and conduct the 2- benzyl of base -1- [4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone -The IRGACURE 369 (BASF AG's system) of 2- dimethylaminos -1- (4- morpholino phenyls) -1- butanone, is respectively relative to three hydroxylsPropane tri adds in 2.5 mass % (amount to 5 mass %), then add in thereto ethyl acetate/cyclohexanone=The mixed solvent of 70/30 [mass ratio], be diluted until solid component concentration be 10 mass %, be modulated into substrate layer formed useCoating fluid.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness, the sheet material (sheet material (ii)) of laminate structures is made.The substrate layer of the sheet material (ii), which contains, to be cross-linked intoPoint, and phase separation structure is formed by irradiating electromagnetic wave i.e. ultraviolet light when ingredient is compatible state, forming structural cycle isThe phase separation structure of 0.003 μm of co-continuous structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.For the present embodimentSubstrate layer in inorganic matter laminate film passes through the irradiation electricity when the substrate layer constituent containing crosslinking component is compatible stateMagnetic wave, that is, ultraviolet light and form phase separation structure, formed and be total to embodiment B13 structure compared periods smaller (for 0.003 μm)The phase separation structure of continuous structure.In addition, inorganic layer is [inorganic A] layer, the inorganic matter laminate film of the present embodiment is with implementingExample B12 is small compared to the structural cycle of the phase separation structure of substrate layer, can adjust barrier properties for gases.
(embodiment B15)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment B10, the sheet material (sheet material of laminate structures is made with 1 μm of formation substrate layer of thickness on base material(ii)), the substrate layer contains crosslinking component, and is formed by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible statePhase separation structure forms the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Other than making thickness for 120nm, identically with embodiment B6, formed on the substrate layer of the above sheet (ii)[inorganic A] layer is as inorganic layer.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.In addition, inorganic layerIt is [inorganic A] layer, the inorganic matter laminate film of the present embodiment is by changing the thickness of inorganic layer, the energy compared with embodiment B10Enough adjust barrier properties for gases.
(embodiment B16)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment B10, the sheet material (sheet material of laminate structures is made with 1 μm of formation substrate layer of thickness on base material(ii)), the substrate layer contains crosslinking component, and is formed by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible statePhase separation structure forms the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Other than making thickness for 100nm, identically with embodiment B6, formed on the substrate layer of the above sheet (ii)[inorganic A] layer is as inorganic layer.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.In addition, inorganic layerIt is [inorganic A] layer, the inorganic matter laminate film of the present embodiment is by changing the thickness of inorganic layer, compared with embodiment B10,15Barrier properties for gases can be adjusted.
(embodiment B17)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment B10, the sheet material (sheet material of laminate structures is made with 1 μm of formation substrate layer of thickness on base material(ii)), the substrate layer contains crosslinking component, and is formed by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible statePhase separation structure forms the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Other than making thickness for 50nm, identically with embodiment B6, [nothing is formed on the substrate layer of the above sheet (ii)Machine A] layer is as inorganic layer.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.In addition, inorganic layer[inorganic A] layer, the inorganic matter laminate film of the present embodiment by changing the thickness of inorganic layer, with embodiment B10, B15,B18, which is compared, can adjust barrier properties for gases.
(embodiment B18)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment B10, the sheet material (sheet material of laminate structures is made with 1 μm of formation substrate layer of thickness on base material(ii)), the substrate layer contains crosslinking component, and by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible state and shapeInto phase separation structure, the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm is formed.
(formation of inorganic layer)
Other than making thickness for 15nm, identically with embodiment B6, [nothing is formed on the substrate layer of the above sheet (ii)Machine A] layer is as inorganic layer.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.In addition, inorganic layer[inorganic A] layer, the inorganic matter laminate film of the present embodiment by making the thickness of inorganic layer thinning, with embodiment B10, B15,B16, B17 are poor compared to barrier properties for gases.
(embodiment B19)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment B10, the sheet material (sheet material of laminate structures is made with 1 μm of formation substrate layer of thickness on base material(ii)), the substrate layer contains crosslinking component, and by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible state and shapeInto phase separation structure, the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm is formed.
(formation of inorganic layer)
Prepare the agglomerated material i.e. sputtering target (molar composition ratio=zinc sulphide/dioxy formed by zinc sulphide and silicaSiClx=80/20), it is arranged in sputtering CVD device.
The vacuum degree of above-mentioned sputtering CVD device is made to be 2 × 10 next, importing argon gas-1Pa is applied using high frequency electric sourceInput electric power 500W, thus generates argon plasma, by sputter on above-mentioned substrate layer formed [inorganic B] layer be used as it is inorganicNitride layer, the thickness for making layer are 150nm.The composition of the inorganic layer is：ZnS is 86.7 mass %, SiO2For 13.3 mass %.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.In addition, inorganic layerIt is [inorganic B] layer, the inorganic matter laminate film of the present embodiment in substrate layer by having phase separation structure, with following comparative example B3((compatible state) sheet material for not had phase separation structure using substrate layer) is compared, and shows higher barrier properties for gases, separatelyEven if being outside the inorganic layer different from embodiment B10, high gas-obstructing character is also showed that.
(embodiment B20)
(formation of the substrate layer of sheet material (ii))
Identically with embodiment B10, the sheet material (sheet material of laminate structures is made with 1 μm of formation substrate layer of thickness on base material(ii)), the substrate layer contains crosslinking component, and by irradiating electromagnetic wave, that is, ultraviolet light when ingredient is compatible state and shapeInto phase separation structure, the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm is formed.
(formation of inorganic layer)
Prepare the evaporation material containing aluminium, be placed in vacuum deposition apparatus.
Next, using above-mentioned vacuum deposition apparatus, by resistance heating manner by aluminium steam, importing oxygen passes throughVacuum vapour deposition forms the layer for containing aluminium compound as inorganic layer on above-mentioned substrate layer, and the thickness for making layer is 20nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.In addition, inorganic layerIt is the layer containing aluminium compound, the inorganic matter laminate film of the present embodiment is and following by having phase separation structure in substrate layerComparative example B4 ((compatible state) sheet material for not had phase separation structure using substrate layer) is compared, and shows higher gas resistanceEvery property.
(embodiment B21)
(formation of the substrate layer of sheet material (ii))
As base material, prepare the poly (ethylene naphthalate) film of 50 μm of thickness.
Next, identically with embodiment B10, with 1 μm of piece for forming substrate layer, laminate structures being made of thickness on base materialMaterial (sheet material (ii)), the substrate layer contains crosslinking component, and passes through the irradiation electromagnetic wave purple when ingredient is compatible stateOutside line forms phase separation structure, forms the phase separation structure for the co-continuous structure that structural cycle is 0.051 μm.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicObject laminate film is different from embodiment B10, using the base material formed by poly (ethylene naphthalate) film, on the substrate with realityApply a B10 similarly laminated substrate layer and inorganic layer.Even if changing base material, high gas-obstructing character is also showed that.
(embodiment B22)
(formation of the substrate layer of sheet material (ii))
As base material, prepare cycloolefin copolymer resin film (Gunze (strain) systems, the trade name of 100 μm of thickness：" F films " F1).
Next, identically with embodiment B10, with 1 μm of formation substrate layer of thickness on base material, the piece of laminate structures is madeMaterial (sheet material (ii)), the substrate layer contains crosslinking component, and passes through the irradiation electromagnetic wave purple when ingredient is compatible stateOutside line and form phase separation structure, formed structural cycle be 0.051 μm co-continuous structure phase separation structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicObject laminate film is different from embodiment B10, using the base material formed by cycloolefin copolymer resin film, on the substrate with embodimentB10 similarly laminated substrate layer and inorganic layer.Even if changing base material also shows that high gas-obstructing character.
(embodiment B23)
(formation of the substrate layer of sheet material (ii))
As base material, prepare cycloolefin resin film (Japanese Zeon (strain) system, the trade name of 100 μm of thickness：" Zeonor films "(registered trademark) ZF-16).
Next, identically with embodiment B10, with 1 μm of formation substrate layer of thickness on base material, the piece of laminate structures is madeMaterial (sheet material (ii)), the substrate layer contains crosslinking component, and passes through the irradiation electromagnetic wave purple when ingredient is compatible stateOutside line and form phase separation structure, formed structural cycle be 0.051 μm co-continuous structure phase separation structure.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on the substrate layer of the above sheet (ii), madeThe thickness of layer is 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.The present embodiment it is inorganicObject laminate film is different from embodiment B10, using the base material formed by cycloolefin resin film, on the substrate with embodiment B10Similarly laminated substrate layer and inorganic layer.Even if changing base material also shows that high gas-obstructing character.
(comparative example B1)
(formation of the substrate layer of sheet material)
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, only prepare pentaerythritol tetraacrylate, then draw as photopolymerizationAgent is sent out, adds 907 (BASF AG of IRGACURE as 2- methyl-1s-[4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetoneSystem) and 369 (BASF AG of IRGACURE as 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) -1- butanoneSystem), it is respectively relative to pentaerythritol tetraacrylate and adds 2.5 mass % (amounting to 5 mass %), then add in acetic acid theretoThe mixed solvent of ethyl ester/cyclohexanone=70/30 [mass ratio], be diluted until solid component concentration be 10 mass %, modulationInto the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, after 80 DEG C of heat dryings 30 seconds, with 0.8J/cm2Irradiation ultraviolet light makes its polymerization, shapeInto 1 μm of substrate layer of thickness.The substrate layer does not form phase separation structure.
(formation of inorganic layer)
Identically with embodiment B1, the layer for containing silicon compound is formed on above-mentioned substrate layer as inorganic layer, makes layerThickness be 100nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.This comparative example it is inorganicObject laminate film laminated inorganic layer containing silicon compound on the substrate layer without phase separation structure, with dividing with phaseIt is compared from embodiment B1~B5 that inorganic layer is identically formed on the substrate layer of structure, barrier properties for gases is poor.
(comparative example B2)
(formation of the substrate layer of sheet material)
Identically with comparative example B1, with the 1 μm of substrate layer of formation without phase separation structure of thickness on base material.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on above-mentioned substrate layer, the thickness for making layer is150nm。
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.This comparative example it is inorganicObject laminate film laminated inorganic layer formed by [inorganic A] layer on the substrate layer without phase separation structure, withEmbodiment B6~embodiment B17, B21, B22, B23 phase of inorganic layer is identically formed on the substrate layer of phase separation structureThan barrier properties for gases is poor.
(comparative example B3)
(formation of the substrate layer of sheet material)
Identically with comparative example B1, with the 1 μm of substrate layer of formation without phase separation structure of thickness on base material.
(formation of inorganic layer)
Identically with embodiment B19, [inorganic B] layer is formed on above-mentioned substrate layer as inorganic layer, makes the thickness of layerFor 150nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.This comparative example it is inorganicObject laminate film laminated inorganic layer formed by [inorganic B] layer on the substrate layer without phase separation structure, withThe embodiment B19 that inorganic layer is identically formed on the substrate layer of phase separation structure is compared, and barrier properties for gases is poor.
(comparative example B4)
(formation of the substrate layer of sheet material)
Identically with comparative example B1, with the 1 μm of substrate layer of formation without phase separation structure of thickness on base material.
(formation of inorganic layer)
Identically with embodiment B20, the layer for containing aluminium compound is formed on above-mentioned substrate layer as inorganic layer, makes layerThickness be 20nm.
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.This comparative example it is inorganicObject laminate film laminated inorganic layer containing aluminium compound on the substrate layer without phase separation structure, with dividing with phaseIt is compared from the embodiment B20 that inorganic layer is identically formed on the substrate layer of structure, barrier properties for gases is poor.
(comparative example B5)
(formation of the substrate layer of sheet material)
As base material, prepare polyethylene terephthalate film (eastern beautiful (strain) system, the trade name of 50 μm of thickness：" Lumirror " (registered trademark) U48)).
Next, as substrate layer formation ingredient, to form as methyl methacrylate/polystyrene=50/50 [matterAmount ratio] mode mixed, then relative to methyl methacrylate add 0.5 mass % azodiisobutyronitriles as hot polymerizationClose initiator, then thereto add in toluene/acetone=50/50 [mass ratio] mixed solvent, be diluted until solid-state intoDivide a concentration of 10 mass %, be modulated into the coating fluid of substrate layer formation.
Next, by micro gravure coating method (intaglio plate wire size 80R, intaglio plate speed ratio 100%) by above-mentioned substrate layer shapeInto coating solution on base material, make within 60 minutes its polymerization in 80 DEG C of heating, form the substrate layer of 1 μm of thickness.The substrateIn addition layer is morphogenetic by the non-conforming shape of ingredient, forms the island structure that structural cycle is 104 μm without crosslinking componentPhase separation structure.It should be noted that even if the structural cycle is measured using A methods also above 100 μm.
(formation of inorganic layer)
Identically with embodiment B6, [inorganic A] layer is formed as inorganic layer on above-mentioned substrate layer, the thickness for making layer is150nm。
(inorganic matter laminate film)
Laminated substrate layer, inorganic layer on base material as described above, obtain inorganic matter laminate film.This comparative example it is inorganicAlthough object laminate film substrate layer has the phase separation structure of island structure, structural cycle is 104 μm, than desired modelIt encloses greatly, therefore, compared with embodiment B6, even if being identically formed inorganic layer, barrier properties for gases is also poor.
Industrial availability
The sheet material of the present invention can control the structure of inorganic compound layer in the layer for forming inorganic compound, hinder gasIt is improved every property, therefore such as food, pharmaceutical packing purposes, solar cell and touch panel, electricity can be preferably applied toThe display bodies such as sub- paper, liquid crystal display, organic el display, organic EL illuminating, but purposes is not limited to this.
Symbol description
1：Surface with dispersed structure
2：Inorganic layer
3a：Substrate layer with dispersed structure
3b：Base material
4：The sheet material (sheet material (i)) of single layer structure with dispersed structure
5：The sheet material (sheet material (ii)) of laminate structures with dispersed structure
6：Continuous phase A in the phase separation structure of co-continuous structure
7：Continuous phase B in the phase separation structure of co-continuous structure
8：Marine facies A in the phase separation structure of island structure
9：Island phase B in the phase separation structure of island structure
10：Phase A in the phase separation structure of column phase structure
11：Phase B in the phase separation structure of column phase structure
12：Phase A in the phase separation structure of Gyroid phase structures
13：Phase B in the phase separation structure of Gyroid phase structures
14：Phase A in the phase separation structure of lamellar phase structure
15：Phase B in the phase separation structure of lamellar phase structure